Benzofluorene compound, emission materials and organic electroluminescent device

ABSTRACT

Provided is a benzofluorene compound which exhibits excellent performances when applied to an organic electroluminescent device. 
     In the benzofluorene compound, a central five-membered ring in a benzofluorene skeleton is substituted with aryl, and a benzene ring condensed to the five-membered ring is substituted with aryl, diarylamino and the like.

FIELD OF THE INVENTION

The present invention relates to a benzofluorene compound, a materialfor an emission layer using the compound and an organicelectroluminescent device.

BACKGROUND OF THE INVENTION

An organic electroluminescent device is a light emitting device which isa spontaneous emission type and is expected as a light emitting devicefor display or lighting. A display unit using an electroluminescentlight emitting device has so far been researched in various casesbecause of possibility of small power consumption and reduction in athickness. Further, an organic electroluminescent device comprisingorganic materials has so far been actively investigated since reductionin a weight and increase in a size are easy. In particular, developmentsof organic materials having light emitting characteristics including ablue color which is one of three primary colors and developments oforganic materials endowed with charge transport ability (havingpossibility of being derived into semiconductors and superconductors) ofholes and electrons have so far been actively researched regardless ofhigh molecular compounds and low molecular compounds.

An organic electroluminescent device has a structure comprising a pairof electrodes comprising an anode and a cathode and a single layer orplural layers which are disposed between a pair of the electrodes andwhich contain organic compounds. The layer containing organic compoundsincludes an emission layer and a charge transport/injection layer whichtransports or injects charges such as a hole and an electron, andvarious organic materials have been developed as the organic compounds(for example, International Publication No. 2004/061047 pamphlet andInternational Publication No. 2004/061048 pamphlet (JP H18-512395(through PCT) A/2006): refer to a patent document 1 and a patentdocument 2). However, only high molecular compounds of benzofluorene aredisclosed in the examples of the patent documents. Also, InternationalPublication No. 2003/051092 pamphlet (JP H17-513713 (through PCT)A/2005), for example, describes dibenzofluorene compounds having aminosubstituted with aryls (refer to a patent document 3). However, thedocument describes only structural formulas thereof, and does notdescribe the specific characteristics thereof.

Patent document 1: International Publication No. 2004/061047 pamphletPatent document 2: International Publication No. 2004/061048 pamphlet(JP H18-512395 (through PCT) A/2006)Patent document 3: International Publication No. 2003/051092 pamphlet(JP H17-513713 (through PCT) A/2005)

However, even if the organic materials described above are used, organicelectroluminescent devices having satisfactory performances in terms ofheat resistance, luminous efficiency, current efficiency, device lifeand external quantum efficiency have not yet been obtained. Under thesituation described above, desired to be developed is an organicelectroluminescent device having further better performances in terms ofheat resistance, luminous efficiency, current efficiency, device lifeand external quantum efficiency, that is, a compound which can providethe device.

Further, in order to meet commercial production of light emittingdevices, desired are organic materials which are more easily synthesizedand organic materials which can accept any processing conditions inapplying to devices. For example, organic materials having an excellentsolubility in a solvent are relatively easily synthesized and have themerit that they are not limited to a vapor deposition method in forminglayers.

SUMMARY OF THE INVENTION

Intensive investigations repeated by the present inventors in order tosolve the problems described above have resulted in successfullyproducing a benzofluorene compound represented by Formula (1) shownbelow. Further, the present inventors have found that an organicelectroluminescent device which is improved in luminous efficiency,current efficiency, device life and external quantum efficiency isobtained by disposing a layer containing the benzofluorene compoundbetween a pair of electrodes to constitute the organicelectroluminescent device, and thus they have completed the presentinvention.

That is, the present invention provides the following benzofluorenecompound.

[1] A benzofluorene compound represented by the following Formula (1):

(wherein Ar¹ and Ar² are aryl which may be substituted;R¹ and R² each are independently hydrogen, alkyl which may besubstituted, cycloalkyl which may be substituted or aryl which may besubstituted, and at least one of R¹ and R² is aryl which may besubstituted).

[2] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are aryl having 6 to 30 carbon atoms which may be substituted;

R¹ and R² each are independently hydrogen, alkyl having 1 to 24 carbonatoms which may be substituted, cycloalkyl having 3 to 12 carbon atomswhich may be substituted or aryl having 6 to 30 carbon atoms which maybe substituted, and at least one of R¹ and R² is aryl having 6 to 30carbon atoms which may be substituted; andsubstituents in Ar¹, Ar², R¹ and R² each are independently alkyl having1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms or arylhaving 6 to 30 carbon atoms.

[3] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are aryl having 6 to 16 carbon atoms which may be substituted;

R¹ and R² are aryl having 6 to 24 carbon atoms which may be substituted;andsubstituents in Ar¹, Ar², R¹ and R² each are independently alkyl having1 to 12 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or arylhaving 6 to 20 carbon atoms.

[4] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are aryl having 6 to 12 carbon atoms which may be substituted;

R¹ and R² are aryl having 6 to 20 carbon atoms which may be substituted;andsubstituents in Ar¹, Ar², R¹ and R² each are independently methyl,ethyl, propyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl,biphenylyl or naphthyl.

[5] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²each are independently phenyl or biphenylyl; and

R¹ and R² each are independently phenyl, biphenylyl, terphenylyl,quaterphenylyl, naphthyl or phenanthryl.

[6] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are aryl having 6 to 16 carbon atoms which may be substituted;

one of R¹ and R² is hydrogen, and the other is aryl having 6 to 24carbon atoms which may be substituted; andsubstituents in Ar¹, Ar², R¹ and R² each are independently alkyl having1 to 12 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or arylhaving 6 to 20 carbon atoms.

[7] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are aryl having 6 to 12 carbon atoms which may be substituted;

one of R¹ and R² is hydrogen, and the other is aryl having 6 to 20carbon atoms which may be substituted; andsubstituents in Ar¹, Ar², R¹ and R² each are independently methyl,ethyl, propyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl,biphenylyl or naphthyl.

[8] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²each are independently phenyl or biphenylyl; and

one of R¹ and R² is hydrogen, and the other is phenyl, biphenylyl,terphenylyl, quaterphenylyl, naphthyl or phenanthryl.

[9] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are phenyl;

R¹ is 4-biphenylyl, and R² is 4-biphenylyl.

[10] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are phenyl;

R¹ is 2-naphthyl, and R² is 2-naphthyl.

[11] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are phenyl;

R¹ is 4-biphenylyl, and R² is 2-naphthyl.

[12] The benzofluorene compound as described in [1], wherein Ar¹ and Ar²are phenyl;

R¹ is 2-naphthyl, and R² is 4-biphenylyl.

[13] A benzofluorene compound represented by the following Formula (1′):

(wherein Ar¹ and Ar² are aryl which may be substituted;R¹ is diarylamino having aryl which may be substituted; andR² is hydrogen, alkyl which may be substituted, cycloalkyl which may besubstituted, aryl which may be substituted or diarylamino having arylwhich may be substituted).

[14] The benzofluorene compound as described in [13], wherein Ar¹ andAr² are aryl having 6 to 30 carbon atoms which may be substituted;

R¹ is diarylamino having aryl having 6 to 30 carbon atoms which may besubstituted;R² is hydrogen, alkyl having 1 to 24 carbon atoms which may besubstituted, cycloalkyl having 3 to 12 carbon atoms which may besubstituted, aryl having 6 to 30 carbon atoms which may be substitutedor diarylamino having aryl having 6 to 30 carbon atoms which may besubstituted; andsubstituents in Ar¹, Ar², R¹ and R² each are independently alkyl having1 to 24 carbon atoms, aryl having 6 to 30 carbon atoms or heteroarylhaving 2 to 30 carbon atoms.

[15] The benzofluorene compound as described in [13], wherein Ar¹ andAr² are aryl having 6 to 16 carbon atoms which may be substituted;

R¹ is diarylamino having aryl having 6 to 16 carbon atoms which may besubstituted;R² is hydrogen, aryl having 6 to 24 carbon atoms which may besubstituted or diarylamino having aryl having 6 to 16 carbon atoms whichmay be substituted; andsubstituents in Ar¹, Ar², R¹ and R² each are independently alkyl having1 to 12 carbon atoms, aryl having 6 to 12 carbon atoms or heteroarylhaving 2 to 10 carbon atoms.

[16] The benzofluorene compound as described in [13], wherein Ar¹ andAr² are aryl having 6 to 12 carbon atoms which may be substituted;

R¹ is diarylamino having aryl having 6 to 12 carbon atoms which may besubstituted;R² is hydrogen, aryl having 6 to 20 carbon atoms which may besubstituted or diarylamino having aryl having 6 to 12 carbon atoms whichmay be substituted; andsubstituents in Ar¹, Ar², R¹ and R² each are independently methyl,ethyl, propyl, t-butyl, phenyl, biphenylyl, naphthyl, pyridyl orthienyl.

[17] The benzofluorene compound as described in [13], wherein Ar¹ andAr² each are independently phenyl or biphenylyl;

R¹ is diphenylamino, dibiphenylamino, dinaphthylamino orphenylnaphthylamino; andR² is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl,phenanthryl, diphenylamino, dibiphenylamino, dinaphthylamino orphenylnaphthylamino.

[18] The benzofluorene compound as described in [13], wherein Ar¹ andAr² are phenyl; and

R¹ and R² are diphenylamino.

[19] A material for an emission layer in a light emitting device andwhich contains the benzofluorene compound as described in any of [1] to[18].

[20] The material for an emission layer as described in [19], furthercontaining at least one selected from the group consisting of perylenederivatives, borane derivatives, amine-containing styryl derivatives,aromatic amine derivatives, coumarin derivatives, pyran derivatives,iridium complexes and platinum complexes.

[21] An organic electroluminescent device comprising a pair ofelectrodes comprising an anode and a cathode and an emission layer whichis disposed between a pair of the electrodes and which contains thematerial for an emission layer as described in [19] or [20].

[22] The organic electroluminescent device as described in [21], furthercomprising an electron transport layer and/or an electron injectionlayer disposed between the cathode and the emission layer, wherein atleast one of the electron transport layer and electron injection layercontains at least one selected from the group consisting of quinolinolmetal complexes, pyridine derivatives and phenanthroline derivatives.

[23] The organic electroluminescent device as described in [21], furthercomprising an electron transport layer and/or an electron injectionlayer disposed between the cathode and the emission layer, wherein atleast one of the electron transport layer and electron injection layercontains quinolinol metal complexes.

[24] The organic electroluminescent device as described in [21], furthercomprising an electron transport layer and/or an electron injectionlayer disposed between the cathode and the emission layer, wherein atleast one of the electron transport layer and electron injection layercontains pyridine derivatives.

[25] The organic electroluminescent device as described in [21], furthercomprising an electron transport layer and/or an electron injectionlayer disposed between the cathode and the emission layer, wherein atleast one of the electron transport layer and electron injection layercontains phenanthroline derivatives.

[26] A display unit comprising the organic electroluminescent device asdescribed in any of [21] to [25].

[27] A lighting instrument comprising the organic electroluminescentdevice as described in any of [21] to [25].

According to the preferred embodiment of the present invention, forexample, a benzofluorene compound having excellent characteristics as amaterial for an emission layer can be provided. Also, an organicelectroluminescent device which is improved in heat resistance, luminousefficiency, current efficiency, device life and external quantumefficiency can be provided. Further, the benzofluorene compoundaccording to the preferred embodiment of the present invention is anorganic material having an excellent solubility in a solvent andtherefore is relatively readily synthesized, and it has the merit thatit is not limited to a vapor deposition method in forming layers. As aresult thereof, a material for a light emitting device which is suitedto commercial production of light emitting devices can be provided.

DETAILED DESCRIPTION OF THE INVENTION

The benzofluorene compound of the present invention shall be explainedin details.

The benzofluorene compound according to the present invention is thebenzofluorene compound represented by Formula (1) described above.

1. Benzofluorene Compound Represented by Formula (1)

First, the benzofluorene compound represented by Formula (1) shall beexplained.

“Aryl” of “aryl which may be substituted” in Ar¹, Ar², R¹ and R² ofFormula (1) includes, for example, aryl having 6 to 30 carbon atoms.“Aryl” in Ar¹ and Ar² is preferably aryl having 6 to 16 carbon atoms,more preferably aryl having 6 to 12 carbon atoms. “Aryl” in R¹ and R² ispreferably aryl having 6 to 24 carbon atoms, more preferably aryl having6 to 20 carbon atoms and further preferably aryl having 6 to 12 carbonatoms.

The specific “aryl” includes phenyl, (o-, m- or p-)tolyl, (2,3-, 2,4-,2,5-, 2,6-, 3,4- or 3,5-)xylyl, mesityl and (o-, m- or p-)cumenyl whichare monocyclic aryls, (2-, 3- or 4-)biphenylyl which is dicyclic aryl,(1- or 2-)naphthyl which is condensed dicyclic aryl,terphenylyl(m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl,o-terphenyl-3′-yl, o-terphenyl-4′-yl, p-terphenyl-2′-yl,m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl,o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yland p-terphenyl-4-yl) which are tricyclic aryls, acenaphthylene-(1-, 3-,4- or 5-)yl, fluorene-(1-, 2-, 3-, 4- or 9-)yl, phenalene-(1- or 2-)yland (1-, 2-, 3-, 4- or 9-)phenanthryl which are condensed tricyclicaryls, quaterphenylyl (5′-phenyl-m-terphenyl-2-yl,5′-phenyl-m-terphenyl-3-yl, 5′-phenyl-m-terphenyl-4-yl andm-quaterphenylyl) which are tetracyclic aryls, triphenylene-(1- or2-)yl, pyrene-(1-, 2- or 4-)yl and naphthacene-(1-, 2- or 5-)yl whichare condensed tetracyclic aryls, perylene-(1-, 2- or 3-)yl andpentacene-(1-, 2-, 5- or 6-)yl which are condensed pentacyclic aryls andthe like.

The particularly preferred “aryl” in Ar¹ and Ar² is phenyl and4-biphenylyl. Ar¹ and Ar² may be the same or different, and Ar¹ and Ar²are preferably the same. If Ar¹ and Ar² are aryl, the benzofluorenecompound represented by Formula (1) is characterized by that it isincreased in rigidity and excellent in heat resistance and that it isextended in life.

The particularly preferred “aryl” in R¹ and R² is phenyl, biphenylyl,terphenylyl, quaterphenylyl, naphthyl and phenanthryl, and among them,phenyl, 4-biphenylyl, 1-naphthyl and 2-naphthyl are preferred. R¹ and R²may be the same or different, and R¹ and R² are preferably the same. IfR¹ and R² are aryl, the benzofluorene compound represented by Formula(1) is characterized by that it is excellent in heat resistance,luminous efficiency and life.

“Alkyl” of “alkyl which may be substituted” in R¹ and R² of Formula (1)may be either linear or branched and includes, for example, linear alkylhaving 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbonatoms. The preferred “alkyl” is alkyl having 1 to 18 carbon atoms(branched alkyl having 3 to 18 carbon atoms). More preferred “alkyl” isalkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbonatoms). Further preferred “alkyl” is alkyl having 1 to 6 carbon atoms(branched alkyl having 3 to 6 carbon atoms). Particularly preferred“alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to4 carbon atoms).

The specific “alkyl” includes methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl,t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl,2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl,2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl,2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl,1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and thelike.

“Cycloalkyl” of “cycloalkyl which may be substituted” in R¹ and R² ofFormula (1) includes, for example, cycloalkyl having 3 to 12 carbonatoms. The preferred “cycloalkyl” is cycloalkyl having 3 to 10 carbonatoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbonatoms. Further preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbonatoms.

The specific “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl,cyclooctyl, dimethylcyclohexyl and the like.

The “substituents” in Ar¹, Ar², R¹ and R² of Formula (1) include alkyl,cycloalkyl and aryl, and the preferred groups thereof include the samegroups as the groups explained in the column of the “alkyl” in R¹ andR², the groups explained in the column of the “cycloalkyl” in R¹ and R²and the groups explained in the column of the “aryl” in Ar¹, Ar², R¹ andR².

The “substituents” in Ar¹, Ar², R¹ and R² include, to be specific, alkylsuch as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl,t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, n-heptyl,n-octyl, t-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl andthe like; cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl and the like; aryl such as phenyl,biphenylyl, naphthyl, terphenylyl, phenanthryl and the like; andalkylaryl such as methylphenyl, ethylphenyl, s-butylphenyl,t-butylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 1,6-dimethylnaphthyl,2,6-dimethylnaphthyl, 4-t-butylnaphthyl and the like. The number of thesubstituents is, for example, a maximum substitutable number, and it ispreferably 0 to 3, more preferably 0 to 2 and further preferably 0(non-substituted).

The specific examples of the compound represented by Formula (1)described above include, for example, compounds represented by thefollowing Formulas (I-1) to (1-86). Among the compounds shown below,particularly preferred are the compounds represented by the followingFormula (1-1), Formula (1-3), Formula (1-4), Formula (1-7), Formula(1-12), Formula (1-13), Formula (1-14), Formula (1-19), Formula (1-23),Formula (1-24), Formula (1-29), Formula (1-31), Formula (1-33), Formula(1-34), Formula (1-41), Formula (1-43), Formula (1-44), Formula (1-49),Formula (1-51), Formula (1-53), Formula (1-54), Formula (1-59), Formula(1-61), Formula (1-63), Formula (1-64), Formula (1-65), Formula (1-84)and Formula (1-86). Further, more preferred are the compoundsrepresented by the following Formula (1-1), Formula (1-4), Formula(1-7), Formula (1-12), Formula (1-13), Formula (1-14), Formula (1-24),Formula (1-29), Formula (1-31), Formula (1-34), Formula (1-44), Formula(1-59), Formula (1-61), Formula (1-63) and Formula (1-65).

2. Benzofluorene Compound Represented by Formula (1′)

Next, the benzofluorene compound represented by Formula (1′) shall beexplained.

Explanations in Ar¹ and Ar² of Formula (1) can be quoted for “aryl whichmay be substituted” in Ar¹ and Ar² of Formula (1′). Further,explanations in R¹ and R² of Formula (1) can be quoted for “alkyl whichmay be substituted”, “cycloalkyl which may be substituted” and “arylwhich may be substituted” in R² of Formula (1′).

“Diarylamino having aryl which may be substituted” in R¹ and R² ofFormula (1′) is amino substituted with two “aryls which may besubstituted”. The “aryls which may be substituted” may be the same ordifferent, and they are preferably the same. “Aryl” of “aryl which maybe substituted” includes, for example, aryl having 6 to 30 carbon atoms,and it includes preferably aryl having 6 to 24 carbon atoms, morepreferably aryl having 6 to 20 carbon atoms, further preferably arylhaving 6 to 16 carbon atoms and particularly preferably aryl having 6 to12 carbon atoms.

To be specific, “aryl” of “aryl which may be substituted” includes, forexample, the “aryls” described above, and more preferred “aryl” isphenyl, biphenylyl, naphthyl and the like, and the particularlypreferred “aryl” is phenyl.

The “substituents” for “aryl which may be substituted” are alkyl, aryl,heteroaryl or the like, and the preferred examples of the alkyl and thearyl include the “alkyls” and the “aryls” each described above. Further,the preferred examples of heteroaryl include the following groups.

The “heteroaryl” includes, for example, heteroaryl having 2 to 30 carbonatoms. The preferred “heteroaryl” is heteroaryl having 2 to 25 carbonatoms, and it is more preferably heteroaryl having 2 to 20 carbon atoms,further preferably heteroaryl having 2 to 15 carbon atoms andparticularly preferably heteroaryl having 2 to 10 carbon atoms.

Further, the “heteroaryl” includes, for example, heterocyclic groupscontaining 1 to 5 hetero atoms selected from oxygen atoms, sulfur atomsand nitrogen atoms other than carbon atoms as ring constitutional atoms,and it includes, for example, aromatic heterocyclic groups.

The “heterocyclic group” includes, for example, pyrrolyl, oxazolyl,isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl,thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl,pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl,benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl,quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl,naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl,phenoxazinyl, phenothiazinyl, phenazinyl, indolidinyl and the like, andimidazolyl, pyridyl, carbazolyl and the like are preferred.

The “aromatic heterocyclic group” includes, for example, furyl, thienyl,pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl,pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl,pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl,isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl,benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl,quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl,naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl,phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathienyl, thianthrenyl,indolidinyl and the like, and thienyl, imidazolyl, pyridyl, carbazolyland the like are preferred.

The specific examples of the compound represented by Formula (1′)described above include, for example, compounds represented by thefollowing Formulas (1′-1) to (1′-16). Among the compounds shown below,particularly preferred are the compounds represented by the followingFormula (1′-1), Formula (1′-2), Formula (1′-6), Formula (1′-9) andFormula (1′-15).

3. Production Process for Benzofluorene Compound <Benzofluorene CompoundRepresented by Formula (1)>

The benzofluorene compound represented by Formula (1) can be produced byusing a known synthetic method such as, for example, a Suzuki couplingreaction. The Suzuki coupling reaction is reaction in which aromatichalide or triflate is subjected to coupling with aromatic boronic acidor aromatic boronic ester under the presence of a base using a palladiumcatalyst. A specific example of a reaction route for obtaining thecompound represented by Formula (1) by the reaction is shown below(schemes 1 to 3). Ar¹, Ar², R¹ and R² in the respective schemes are thesame as described above, and Tfo is triflate.

The specific examples of the palladium catalyst used in the reaction arePd(PPh₃)₄, PdCl₂(PPh₃)₂, Pd(OAc)₂, tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)dipalladium (0) chloroform complex,bis(dibenzylideneacetone)palladium (0) and the like. A phosphinecompound may be added, if necessary, to the palladium compounds in orderto accelerate the reaction. The specific examples of the phosphinecompound include tri(t-butyl)phosphine, tricyclohexylphosphine,1-(N,N-dimethylaminomethyl)-2-(di-t-butylphosphino)ferrocene,1-(N,N-dibutylaminomethyl)-2-(di-t-butylphosphino)ferrocene,1-(methoxymethyl)-2-(di-t-butylphosphino)ferrocene,1,1′-bis(di-t-butylphosphino)ferrocene,2,2′-bis(di-t-butylphosphino)-1,1′-binaphthyl,2-methoxy-2′-(di-t-butylphosphino)-1,1′-binaphthyl and the like.

The specific examples of the base used in the reaction are sodiumcarbonate, potassium carbonate, cesium carbonate, sodiumhydrogencarbonate, sodium hydroxide, potassium hydroxide, bariumhydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate,tripotassium phosphate, potassium fluoride and the like.

Further, the specific examples of the solvent used in the reaction arebenzene, toluene, xylene, N,N-dimethylformamide, tetrahydrofuran,diethyl ether, t-butyl methyl ether, 1,4-dioxane, methanol, ethanol,isopropyl alcohol and the like. These solvents can suitably be selectedaccording to the structures of aromatic halide, triflate, aromaticboronic ester and aromatic boronic acid which is subjected to thereaction. The solvent may be used alone or in the form of a mixedsolvent.

<Benzofluorene Compound Represented by Formula (1′)>

When R¹ and R² are diarylamino having aryl which may be substituted inFormula (1′), the benzofluorene compound represented by Formula (1′) canbe produced by using an existing reaction such as a Buchwald-Hartwigreaction or a Ullmann reaction. The Buchwald-Hartwig reaction isreaction in which aromatic halide is subjected to coupling with primaryaromatic amine or secondary aromatic amine under the presence of a baseusing a palladium catalyst or a copper catalyst. A specific example of areaction route for obtaining the compound represented by Formula (1′) bythe reaction is shown below (schemes 4 to 7).

Ar¹ and Ar² in the respective schemes are the same as described above,and R¹ and R² are diarylamino having aryl which may be substituted. R³and R⁴ are “aryl which may be substituted” constituting “diarylaminohaving aryl which may be substituted”.

The specific examples of the palladium catalyst, the base and thesolvent which are used in the reaction can be selected from those usedin the Suzuki coupling reaction. A phosphine compound may be added, ifnecessary, to the palladium compounds in order to accelerate thereaction. The specific examples of the phosphine compound can beselected as well from the same compounds as the specific examples shownin the Suzuki coupling reaction. In addition to the compounds,1,1′-bis(diphenylphosphino)ferrocene, bis(diphenylphosphino)binaphthyland the like can be used as well.

The Ullmann reaction is reaction in which aromatic halide is subjectedto coupling with primary aromatic amine or secondary aromatic amineunder the presence of a base using a copper catalyst. The specificexamples of the copper catalyst used in the reaction are copper powder,copper chloride, copper bromide, copper iodide and the like. Thespecific examples of the base used in the reaction can be selected fromthe same compounds as in the Suzuki coupling reaction. The specificexamples of the solvent used in the reaction are nitrobenzene,dichlorobenzene, N,N-dimethylformamide and the like.

Also, in a case where R¹ is diarylamino having aryl which may besubstituted and where R² is hydrogen, alkyl which may be substituted,cycloalkyl which may be substituted or aryl which may be substituted inFormula (1′), the compound represented by Formula (1′) can be producedby the scheme 5.

In the case, R² in the scheme 5 is hydrogen, alkyl which may besubstituted, cycloalkyl which may be substituted or aryl which may besubstituted. Ar¹ and Ar² in the scheme 5 are the same as describedabove, and R³ and R⁴ are “aryl which may be substituted” constituting“diarylamino having aryl which may be substituted”.

The benzofluorene compounds represented by Formula (1) and Formula (1′)are compounds having strong fluorescence in a solid state and can beused for emission of various colors, and they are suited particularly toemission of a blue color. Among the benzofluorene compounds representedby Formula (1) and Formula (1′), the compounds having an asymmetricmolecular structure are liable to form an amorphous state in producingan organic EL device. Further, they are excellent in heat resistance andstable in applying an electric field.

The benzofluorene compound represented by Formula (1) is effective as ahost emission material. The benzofluorene compound has a shorteremission wavelength, and it is excellent particularly as a blue hostemission material but can be used as well for emission of colors otherthan a blue color. When the benzofluorene compound is used as a hostmaterial, energy transfer is efficiently carried out, and a lightemitting device having high efficiency and long life can be obtained.

Further, the benzofluorene compound represented by Formula (1′) iseffective particularly as a dopant material.

The benzofluorene compounds represented by Formula (1) and Formula (1′)comprise benzo[c]fluorene in a fluorene skeleton and therefore areexcellent in solubility in solvents as compared with compounds having abenzo[α]fluorene skeleton. Accordingly, width in selecting a solvent insynthesis is broad, and therefore freedom of the synthesis can beenhanced, and mass production can be easy. Further a spin coating methodusing various solvents can readily be employed.

The benzofluorene compound represented by Formula (1′) is substitutedwith diaryl amino in a R¹ position without fail. This compound has highheat resistance as compared with the compound substituted with diarylamino only in a R² position, and it is improved in luminous efficiencywhen applied to a device.

4. Organic Electroluminescent Device

The benzofluorene compound according to the present invention can beused, for example, as a material for an organic electroluminescentdevice.

The organic electroluminescent device according to this embodiment shallbe explained in details with reference to a drawing. FIG. 1 is anoutline cross-sectional drawing showing the organic electroluminescentdevice according to the present embodiment.

<Structure of Organic Electroluminescent Device>

An organic electroluminescent device 100 shown in FIG. 1 comprises asubstrate 101, an anode 102 provided on the substrate 101, a holeinjection layer 103 provided on the anode 102, a hole transport layer104 provided on the hole injection layer 103, an emission layer 105provided on the hole transport layer 104, an electron transport layer106 provided on the emission layer 105, an electron injection layer 107provided on the electron transport layer 106 and a cathode 108 providedon the electron injection layer 107.

The organic electroluminescent device 100 may be turned upside down in apreparation order and may assume a structure in which it comprises, forexample, the substrate 101, the cathode 108 provided on the substrate101, the electron injection layer 107 provided on the cathode 108, theelectron transport layer 106 provided on the electron injection layer107, the emission layer 105 provided on the electron transport layer106, the hole transport layer 104 provided on the emission layer 105,the hole injection layer 103 provided on the hole transport layer 104and the anode 102 provided on the hole injection layer 103.

All the respective layers described above do not necessarily have to bepresent, and the hole injection layer 103, the hole transport layer 104,the electron transport layer 106 and the electron injection layer 107are layers which are optionally provided, wherein a minimum structuralunit assumes a structure comprising the anode 102, the emission layer105 and cathode 108. The respective layers described above each maycomprise a single layer or plural layers.

The mode of the layers constituting the organic electroluminescentdevice may be, in addition to the structural mode of“substrate/anode/hole injection layer/hole transport layer/emissionlayer/electron transport layer/electron injection layer/cathode”described above, the structural modes of “substrate/anode/hole transportlayer/emission layer/electron transport layer/electron injectionlayer/cathode”, “substrate/anode/hole injection layer/emissionlayer/electron transport layer/electron injection layer/cathode”“substrate/anode/hole injection layer/hole transport layer/emissionlayer/electron injection layer/cathode”, “substrate/anode/hole injectionlayer/hole transport layer/emission layer/electron transportlayer/cathode”, “substrate/anode/emission layer/electron transportlayer/electron injection layer/cathode”, “substrate/anode/hole transportlayer/emission layer/electron injection layer/cathode”,“substrate/anode/hole transport layer/emission layer/electron transportlayer/cathode”, “substrate/anode/hole injection layer/emissionlayer/electron injection layer/cathode”, “substrate/anode/hole injectionlayer/emission layer/electron transport layer/cathode”,“substrate/anode/hole injection layer/hole transport layer/emissionlayer/cathode”, “substrate/anode/hole injection layer/emissionlayer/cathode”, “substrate/anode/hole transport layer/emissionlayer/cathode”, “substrate/anode/emission layer/electron transportlayer/cathode”, “substrate/anode/emission layer/electron injectionlayer/cathode” and “substrate/anode/emission layer/cathode”.

<Substrate in the Organic Electroluminescent Device>

The substrate 101 is a base for the organic electroluminescent device100, and quartz, glass, metal, plastics and the like are usually usedtherefor. The substrate 101 is formed in the shape of a plate, a film ora sheet according to the purposes, and a glass plate, a metal plate, ametal foil, a plastic film or a plastic sheet is used therefor. Amongthem, a glass plate and a plate made of a transparent synthetic resinsuch as polyester, polymethacrylate, polycarbonate and polysulfone arepreferred. Soda lime glass, non-alkali glass and the like are used forthe glass substrate. The thickness thereof may be such a thickness asenough for maintaining the mechanical strength, and therefore it is, forexample, 0.2 mm or more. An upper limit value of the thickness is, forexample, 2 mm or less, preferably 1 mm or less. The material of glass ispreferably non-alkali glass since ions eluted from glass are preferablyfewer. Soda lime glass which is provided with a barrier coat such asSiO₂ is commercially available, and therefore it can be used. Thesubstrate 101 may be provided at least on one face thereof with a gasbarrier film such as a minute silicon oxide film in order to enhance gasbarrier property thereof. Particularly when a plate, a film or a sheetmade of a synthetic resin having low gas barrier property is used forthe substrate 101, a gas barrier membrane is preferably providedthereon.

<Anode in the Organic Electroluminescent Device>

The anode 102 plays a role of injecting holes into the emission layer105. When the hole injection layer 103 and/or the hole transport layer104 are provided between the anode 102 and the emission layer 105, holesare injected into the emission layer 105 via these layers.

A material for forming the anode 102 includes inorganic compounds andorganic compounds. The inorganic compounds include, for example, metals(aluminum, gold, silver, nickel, palladium, chromium and the like),metal oxides (oxide of indium, oxide of tin, indium-tin oxide (ITO) andthe like), halogenated metals (copper iodide and the like), coppersulfide, carbon black, ITO glass, nesa glass and the like. The organiccompounds include, for example, polythiophene such aspoly(3-methylthiophene) and electrically conductive polymers such aspolypyrrole, polyaniline and the like. In addition thereto, thosesuitably selected from materials used for an anode of an organicelectroluminescent device can be used.

A resistance of the transparent electrode shall not be restricted aslong as an electric current sufficient for emission of the lightemitting device can be supplied, and it is preferably a low resistancefrom the viewpoint of power consumption of the light emitting device.For example, an ITO substrate having a resistance of 300 K/square orless functions as a device electrode. At present, a substrate having aresistance of about 10 Ω/square can be supplied, and therefore a producthaving a low resistance of, for example, 100 to 5 Ω/square, preferably50 to 5 Ω/square is particularly preferably used. A thickness of ITO canoptionally be selected depending on a resistance value thereof, and itis usually used in a range of 100 to 300 nm in many cases.

<Hole Injection Layer and Hole Transport Layer in the OrganicElectroluminescent Device>

The hole injection layer 103 plays a role of efficiently injecting holesmoving from the anode 102 into the emission layer 105 or the holetransport layer 104. The hole transport layer 104 plays a role ofefficiently transporting holes injected from the anode 102 or holesinjected from the anode 102 via the hole injection layer 103 to theemission layer 105. The hole injection layer 103 and the hole transportlayer 104 are formed respectively by laminating or mixing one or morehole injecting or transporting material(s) or from a mixture of the holeinjecting or transporting material(s) with a high molecular binder.Further, inorganic salt such as iron chloride (III) may be added to thehole injecting or transporting material to form the layers.

The hole injecting or transporting material has to efficiently inject ortransport holes from a positive electrode between the electrodes towhich an electrical field is applied, and it is desirable that the holeinjection efficiency is high and that the holes injected are efficientlytransported. Accordingly, preferred is the material which has smallionization potential and large hole mobility and is excellent instability and in which impurities trapped are less liable to begenerated in producing and using.

Optional compounds selected from compounds which have so farconventionally been used as a charge transport material for a hole in aphotoconductive material, p type semiconductors and publicly knowncompounds used for a hole injection layer and a hole transport layer inan organic electroluminescent device can be used as materials forforming the hole injection layer 103 and the hole transport layer 104.The specific examples thereof are preferably carbazole derivatives(N-phenylcarbazole, polyvinylcarbazole and the like), biscarbazolederivatives such as bis(N-allylcarbazole) and bis(N-alkylcarbazole),triarylamine derivatives (polymers having aromatic tertiary amine on amain chain or a side chain), triphenylamine derivatives such as1,1-bis(4-di-p-tolylaminophenyl)cyclohexane,N,N′-diphenyl-N,N′-di(3-methylphenyl)-4,4′-diaminobiphenyl,N,N′-diphenyl-N,N′-dinaphthyl-4,4′-diaminobiphenyl (hereinafterabbreviated as NPD),N,N′-diphenyl-N,N′-di(3-methylphenyl)-4,4′-diphenyl-1,1′-diamine,N,N′-dinaphthyl-N,N′-diphenyl-4,4′-diphenyl-1,1′-diamine and4,4′,4″-tris(3-methylphenyl(phenyl)-amino)triphenylamine, starburstamine derivatives and the like, stilbene derivatives, heterocycliccompounds such as phthalocyanine derivatives (non-metal phthalocyanines,copper phthalocyanine and the like), pyrazoline derivatives, hydrazonecompounds, benzofuran derivatives, thiophene derivatives, oxadiazolederivatives and porphylin derivatives, polysilane and the like. Inpolymer compounds, polycarbonate, styrene derivatives,polyvinylvcarbazole, polysilane and the like which have the monomersdescribed above on side chains are preferred, but they shall notspecifically be restricted as long as they are compounds which can forma thin film necessary for preparing a light emitting device and whichcan inject holes from an anode and can transport the holes.

It is know as well that electrical conductivity of an organicsemiconductor is strongly influenced by doping thereof. Such organicsemiconductor matrix substance is constituted from a compound havinggood electron donating property or a compound having good electronaccepting property. Strong electron acceptors such astetracyanoquinonedimethane (TCNQ) or2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) areknown for doping electron donating substances (refer to, for example, adocument “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202 to 3204 (1998)” and a document “J. Blochwitz, M. Pfeiffer, T.Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729 to 731 (1998)”). Theyproduce so-called holes by an electron moving process in an electrondonating type base material (hole transport material). Conductivity ofthe base material is changed to a considerably large extent by thenumber and mobility of holes. Known as a matrix substance having holetransport property are, for example, benzidine derivatives (TPD and thelike), starburst amine derivatives (TDATA and the like) and specificmetal phthalocyanines (particularly zinc phthalocyanine ZnPc and thelike) (JP H17-167175 A/2005).

<Emission Layer in the Organic Electroluminescent Device>

The emission layer 105 emits light by recombining holes injected fromthe anode 102 with electrons injected from the cathode 108 between theelectrodes to which an electrical field is applied. A material forforming the emission layer 105 may be any compounds as long as they arecompounds (luminescent compounds) which are excited by recombination ofholes with electrons to emit light, and they are preferably compoundswhich can form a stable thin film shape and which show strong emission(luminescence and/or phosphorescence) efficiency in a solid state.

The emission layer may comprise either a single layer or plural layersand is formed by an emission material (host material and dopantmaterial). This may be either a mixture of a host material and a dopantmaterial or a host material alone. That is, only the host material orthe dopant material may emit light or both the host material and thedopant material may emit light in the respective layers of the emissionlayer. The host material and the dopant material each may compriseeither one kind or combination of two or more kinds thereof. The dopantmaterial may be contained in either the whole part or a part of the hostmaterial. A use amount of the dopant is varied depending on the dopantand can be determined so that the use amount meets the characteristicsof the dopant (for example, a too large use amount of the dopant islikely to bring about a concentration quenching phenomenon). A standardof a use amount of the dopant is preferably 0.001 to 50% by weight, morepreferably 0.1 to 10% by weight and further preferably 1 to 5% by weightbased on the whole emission material. In a doping method, the emissionlayer can be formed by a method of co-depositing with the host material,or the dopant material may be mixed in advance with the host materialand then deposited at the same time.

Further, the emission material for the light emitting device accordingto the present embodiment may be either fluorescent or phosphorescent.

The benzofluorene compound represented by Formula (1) described abovecan be used as the host material. In particular, preferably used are thecompounds represented by the foregoing Formula (1-1), Formula (1-3),Formula (1-4), Formula (1-7), Formula (I-12), Formula (1-13), Formula(1-14), Formula (1-19), Formula (1-23), Formula (1-24), Formula (1-29),Formula (1-31), Formula (1-33), Formula (1-34), Formula (1-41), Formula(1-43), Formula (1-44), Formula (1-49), Formula (1-51), Formula (1-53),Formula (1-54), Formula (1-59), Formula (1-61), Formula (1-63), Formula(1-64), Formula (1-65), Formula (1-84) and Formula (1-86). Further, morepreferably used are the compounds represented by the foregoing Formula(1-1), Formula (1-4), Formula (1-7), Formula (1-12), Formula (1-13),Formula (1-14), Formula (1-24), Formula (1-29), Formula (1-31), Formula(1-34), Formula (1-44), Formula (1-59), Formula (1-61), Formula (1-63)and Formula (1-65). A use amount of the benzofluorene compoundrepresented by the foregoing Formula (1) as the host material ispreferably 50 to 99.999% by weight, more preferably 80 to 99.95% byweight and further preferably 90 to 99.9 by weight based on the wholeemission material.

Other host materials shall not specifically be restricted, and suitablyused are condensed ring derivatives such as anthracene, pyrene and thelike which have so far been known as an emission material, metalchelated oxynoid compounds including tris(8-quinolinolate)aluminum,bisstyryl derivatives such as bisstyrylanthracene derivatives,distyrylbenzene derivatives and the like, tetraphenylbutadienederivatives, coumarin derivatives, oxadiazole derivatives,pyrrolopyridine derivatives, perinone derivatives, cyclopentadienederivatives, oxadiazole derivatives, thiadiazolopyridine derivatives,pyrrolopyrrole derivatives and polymers such as polyphenylenevinylenederivatives, polyparaphenylene derivatives and polythiophenederivatives.

In addition to the compounds, compounds suitably selected from compoundsdescribed in Kagaku Kogyo (Chemical Industry) issued in June 2004edition, p. 13 and references cited therein can be used as the hostmaterial.

The benzofluorene compound represented by Formula (1′) described abovecan be used as the dopant material, and in particular, more preferablyused are the compounds represented by the foregoing Formula (1′-1),Formula (1′-2), Formula (1′-6), Formula (1′-9) and Formula (1′-15). Ause amount of the benzofluorene compound represented by the foregoingFormula (1′) as the dopant material is preferably 0.001 to 50% byweight, more preferably 0.05 to 20% by weight and further preferably 0.1to 10% by weight based on the whole emission material. In a dopingmethod, the emission layer can be formed by a method of co-depositingwith the host material, or the dopant material may be mixed in advancewith the host material and then deposited at the same time.

Other dopant materials shall not specifically be restricted, and knowncompounds can be used. They can be selected from various compoundsaccording to emission colors desired. To be specific, they include, forexample, condensed ring derivatives such as phenanthrene, anthracene,pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene,rubrene and the like, benzoxazole derivatives, benzothiazolederivatives, benzimidazole derivatives, benzotriazole derivatives,oxazole derivatives, oxadiazole derivatives, thiazole derivatives,imidazole derivatives, thiadiazole derivatives, triazole derivatives,pyrazoline derivatives, stilbene derivatives, thiophene derivatives,tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylderivatives (JP H1-245087 A/1989) such as bisstyrylanthracenederivatives, distyrylbenzene derivatives and the like, bisstyrylarylenederivatives (JP H2-247278 A/1990), diazaindacene derivatives, furanderivatives, benzofuran derivatives, isobenzofuran derivatives suchphenylisobenzofuran, dimesitylisobenzofuran,di(2-methylphenyl)isobenzofuran,di(2-trifluoromethylphenyl)isobenzofuran, phenylisobenzofuran and thelike, dibenzofuran derivatives, coumarin derivatives-such as7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives,7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives,7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives,3-benzimidazolylcoumarin derivatives, 3-benzoxazolylcoumarin derivativesand the like, dicyanomethylenepyran derivatives,dicyanomethylenethiopyran derivatives, polymethine derivatives, cyaninederivatives, oxobenzanthracene derivatives, xanthene derivatives,rhodamine derivatives, fluorescein derivatives, pyrylium derivatives,carbostyryl derivatives, acridine derivatives, oxazine derivatives,phenylene oxide derivatives, quinacridone derivatives, quinazolinederivatives, pyrrolopyridine derivatives, ferropyridine derivatives,1,2,5-thiadiazolopyrene derivatives, pyrromethene derivatives, perinonederivatives, pyrrolopyrrole derivatives, squarylium derivatives,violanthrone derivatives, phenazine derivatives, acridone derivatives,deazaflavin derivatives and the like.

To give the examples thereof by color of emission, the blue to bluishgreen dopant materials include aromatic hydrocarbon compounds andderivatives thereof such as naphthalene, anthracene, phenanthrene,pyrene, triphenylene, perylene, fluorene, indene and the like, aromaticheterocyclic compounds and derivatives thereof such as furan, pyrrole,thiophene, silole, 9-silafluorene, 9,9′-spirobisilafluorene,benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran,imidazopyridine, phenanthroline, pyrazine, naphthylidine, quinoxaline,pyrrolopyridine, thioxanthene and the like, distyrylbenzene derivatives,tetraphenylbutadiene derivatives, stilbene derivatives, aldazinederivatives, coumarin derivatives, azole derivatives and metal complexesthereof such as imidazole, thiazole, thiadiazole, carbazole, oxazole,oxadiazole, triazole and the like and aromatic amine derivativesrepresented byN,N′-diphenyl-N,N′-di(3-methylphenyl)-4,4′-diphenyl-1,1′-diamine.

The green to yellow dopant materials include coumarin derivatives,phthalimide derivatives, naphthalimide derivatives, perinonederivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives,acridone derivatives, quinacridone derivatives, naphthacene derivatives(such as rubrene) and the like. Further, the suitable examples thereofinclude compounds obtained by introducing substituents which can shiftwavelengths to a longer side such as aryl group(s), heteroaryl group(s),arylvinyl group(s), amino group(s), cyano group(s) and the like into thecompounds given as the examples of the blue to bluish green dopantmaterials described above.

Further, the orange to red dopant materials include naphthalimidederivatives such as bis(diisopropylphenyl)perylene tetracarboxylicimide, perinone derivatives, rare earth complexes such as Eu complexeshaving acetylacetone, benzoylacetone and phenanthroline as ligands,4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran andanalogous compounds thereof, metal phthalocyanine derivatives such asmagnesium phthalocyanine, aluminum chlorophthalocyanine and the like,rhodamine derivatives, deazaflavin derivatives, coumarin derivatives,quinacridone derivatives, phenoxazine derivatives, oxazine derivatives,quinazoline derivatives, pyrrolopyridine derivatives, squaryliumderivatives, violanthrone derivatives, phenazine derivatives,phenoxazone derivatives, thidiazolopyrene and the like. Further, thesuitable examples thereof include compounds obtained by introducingsubstituents which can shift wavelengths to a longer side such as arylgroup(s), heteroaryl group(s), arylvinyl group(s), amino group(s), cyanogroup(s) and the like into the compounds given as the examples of theblue to bluish green and green to yellow dopant materials describedabove. Further, the suitable examples thereof include phosphorescentmetal complexes comprising iridium and platinum as central metalsrepresented by tris(8-phenylpyridine)iridium (III).

Among the dopant materials described above, the dopant materials whichare suited to the material for the emission layer according to thepresent invention are particularly preferably the benzofluorene compoundrepresented by Formula (1′), perylene derivatives, borane derivatives,amine-containing styryl derivatives, aromatic amine derivatives,coumarin derivatives, pyran derivatives, iridium complexes or platinumcomplexes.

The perylene derivatives include, for example,3,10-bis(2,6-dimethylphenyl)perylene,3,10-bis(2,4,6-trimethylphenyl)perylene, 3,10-diphenylperylene,3,4-diphenylperylene, 2,5,8,11-tetra-t-butylperylene,3,4,9,10-tetraphenylperylene, 3-(1′-pyrenyl)-8,11-di(-t-butyl)perylene,3-(9′-anthryl)-8,11-di(-t-butyl)perylene,3,3′-bis(8,11-di(-t-butyl)perylenyl) and the like.

Further, perylene derivatives described in JP H11-97178 A/1999, JPH12-133457 A/2000, JP H12-26324 A/2000, JP H13-267079 A/2001, JPH13-267078 A/2001, JP H13-267076 A/2001, JP H12-34234 A/2000, JPH13-267075 A/2001, JP H13-217077 A/2001 and the like may be used aswell.

The borane derivatives include, for example,1,8-diphenyl-10-(dimesitylboryl)anthracene,9-phenyl-10-(dimesitylboryl)anthracene,4-(9′-anthryl)dimesitylborylnaphthalene,4-(10′-phenyl-9′-anthryl)dimesitylborylnaphthalene,9-(dimesitylboryl)anthracene,9-(4′-biphenylyl-10-(dimesitylboryl)anthracene,9-(4′-(N-carbazolyl)phenyl)-10-(dimesitylboryl)anthracene and the like.

Further, borane derivatives described in International Publication No.2000/40586 pamphlet and the like may be used as well.

The amine-containing styryl derivatives include, for example,N,N,N′,N′-tetra(4-biphenylyl)-4,4′-diaminostilbene,N,N,N′,N′-tetra(1-naphthyl)-4,4′-diaminostilbene,N,N,N′,N′-tetra(2-naphthyl)-4,4′-diaminostilbene,N,N′-di(2-naphthyl)-N,N′-diphenyl-4,4′-diaminostilbene,N,N′-di(9-phenanthryl)-N,N′-diphenyl-4,4′-diaminostilbene,4,4′-bis[4″-bis(diphenylamino)styryl]-biphenyl,1,4-bis[4′-bis(diphenylamino)styryl]-benzene,2,7-bis[4′-bis(diphenylamino)styryl]-9,9-dimethylfluorene,4,4′-bis(9-ethyl-3-carbazovinylene)-biphenyl,4,4′-bis(9-phenyl-3-carbazovinylene)-biphenyl and the like.

Further, amine-containing styryl derivatives described in JP H15-347056A/2003, JP H13-307884 A/2001 and the like may be used as well.

The aromatic amine derivatives include, for example,N,N,N,N-tetraphenylanthracene-9,10-diamine,9,10-bis(4-diphenylamino-phenyl)anthracene,9,10-bis(4-di(1-naphthylamino)phenyl)anthracene,9,10-bis(4-di(2-naphthylamino)phenyl)anthracene,10-di-p-tolylamino-9-(4-di-p-tolylamino-1-naphthyl)anthracene,10-diphenylamino-9-(4-diphenylamino-1-naphthyl)anthracene,10-diphenylamino-9-(6-diphenylamino-2-naphthyl)anthracene,[4-(4-diphenylamino-phenyl)naphthalene-1-yl]-diphenylamine,[4-(4-diphenylamino-phenyl)naphthalene-1-yl]-diphenylamine,[6-(4-diphenylamino-phenyl)naphthalene-2-yl]-diphenylamine,4,4′-bis[4-diphenylaminonaphthalene-1-yl]biphenyl,4,4′-bis[6-diphenylaminonaphthalene-2-yl]biphenyl,4,4″-bis[4-diphenylaminonaphthalene-1-yl]-p-terphenyl,4,4″-bis[6-diphenylaminonaphthalene-2-yl]-p-terphenyl and the like.

Further, aromatic amine derivatives described in JP H18-156888 A/2006and the like may be used as well.

The coumarin derivatives include coumarin-6, coumarin-334 and the like.

Further, coumarin derivatives described in JP H16-43646 A/2004, JPH13-76876 A/2001, JP H6-298758 A/1994 and the like may be used as well.

The pyran derivatives include DCM and DCJTB shown below.

Further, pyran derivatives described in JP H17-126399 A/2005, JPH17-097283 A/2005, JP H14-234892 A/2002, JP H13-220577 A/2001, JPH13-081090 A/2001, JP H13-052869 A/2001 and the like may be used aswell.

The iridium complexes include Ir(ppy)₃ shown below.

Further, iridium complexes described in JP H18-089398 A/2005, JPH18-080419 A/2006, JP H17-298483 A/2005, JP H17-097263 A/2005, JPH16-111379 A/2004 and the like may be used as well.

The platinum complexes include PtOEP shown below.

Further, platinum complexes described in JP H18-190718 A/2006, JPH18-128634 A/2006, JP H18-093542 A/2006, JP H16-335122 A/2004, JPH16-331508 A/2004 and the like may be used as well.

In addition to the compounds, compounds suitably selected from compoundsdescribed in Kagaku Kogyo (Chemical Industry) issued in June 2004edition, p. 13 and references cited therein can be used as the dopantmaterial.

<Electron Injection Layer and Electron Transport layer in the organicelectroluminescent device>

The electron injection layer 107 plays a role of efficiently injectingelectrons moving from the cathode 108 into the emission layer 105 or theelectron transport layer 106. The electron transport layer 106 plays arole of efficiently transporting electrons injected from the cathode 108or electrons injected from the cathode 108 via the electron injectionlayer 107 to the emission layer 105. The electron transport layer 106and the electron injection layer 107 are formed respectively bylaminating or mixing one or more electron transporting or injectingmaterial(s) or from a mixture of the electron transporting or injectingmaterial(s) with a high molecular binder.

An electron injection or transport layer is a layer into which electronsare injected from the cathode and which controls transportation of theelectrons, and it is desirable that the electron injection efficiency ishigh and that the electrons injected are efficiently transported.Accordingly, preferred is the material which has large electron affinityand large electron mobility and is excellent in stability and in whichimpurities trapped are less liable to be generated in producing andusing. However, when considering a transport balance between a hole andan electron, the material is provided, even if electron transportability is not so high, with an effect of enhancing luminous efficiencyto the same extent as that of a material having high electron transportability in the case of playing principally a role of efficientlyinhibiting holes coming from the anode from moving to a cathode sidewithout recombination. Accordingly, the electron injection and transportlayer in the present embodiment may be provided as well with a functionof a layer which can efficiently inhibit holes from moving.

Compounds optionally selected from compounds which have so far beenconventionally used as electron transport materials in photoconductivematerials and publicly known compounds used for an electron injectionlayer and an electron transport layer of an organic electroluminescentdevice can be used as the materials used for the electron transportlayer and the electron injection layer.

To be specific, the compounds include pyridine derivatives, naphthalenederivatives, anthracene derivatives, phenanthroline derivatives,perynone derivatives, coumarin derivatives, naphthalimide derivatives,anthraquinone derivatives, diphenoquinone derivatives, diphenylquinonederivatives, perylene derivatives, thiophene derivatives, thiadiazolederivatives, quinoxaline derivatives, polymers of quinoxalinederivatives, benzazole compounds, pyrazole derivatives, perfluorinatedphenylene derivatives, triazine derivatives, pyrazine derivatives,imidazopyridine derivatives, borane derivatives, benzoxazolederivatives, benzothiazole derivatives, quinoline derivatives, aldazinederivatives, carbazole derivatives, indole derivatives, phosphorus oxidederivatives, bisstyryl derivatives and the like. Further, they includeoxazole derivatives(1,3-bis[(4-t-butylphenyl)-1,3,4-oxadiazolyl]phenylene and the like),triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4-triazole and thelike), benzoquinoline derivatives(2,2′-bis(benzo[h]quinoline-2-yl)-9,9′-spirobifluorene and the like),benzimidazole derivatives (tris(N-phenylbenzimidazole-2-yl)benzene andthe like), bipyridine derivatives, terpyridine derivatives(1,3-bis(4′-(2,2′,:6′,2″-terpyridinyl))benzene and the like),naphthyridine derivatives(bis(1-naphthyl)-4-(1,8-naphthyridine-2-yl)phenylphosphine oxide and thelike) and the like. The materials may be used alone or in a mixture withdifferent materials.

Further, metal complexes having electron accepting nitrogen can be usedas well and include, for example, quinolinol metal complexes,hydroxyazole complexes such as hydroxyphenyloxazole complexes,azomethine complexes, tropolone metal complexes, flavonol metalcomplexes, benzoquinoline metal complexes and the like. The materialsmay be used alone or in a mixture with different materials.

Among the compounds, the quinolinol metal complexes, the pyridinederivatives or the phenanthroline derivatives are preferred.

The quinolinol metal complexes are compounds represented by Formula(E-1) shown below:

wherein R₁ to R₆ are hydrogen or a substituent; M is Al, Ga, Be or Zn;and n is an integer of 2 or 3.

The specific examples of the quinolinol metal complexes includetris(8-quinolinolate)aluminum (hereinafter abbreviated as ALQ),tris(4-methyl-8-quinolinolate)aluminum,tris(5-methyl-8-quinolinolate)aluminum,tris(3,4-dimethyl-8-quinolinolate)aluminum,tris(4,5-dimethyl-8-quinolinolate)aluminum,tris(4,6-dimethyl-8-quinolinolate)aluminum,bis(2-methyl-8-quinolinolate)(phenolate)aluminum,bis(2-methyl-8-quinolinolate)(2-methylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(3-methylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(4-methylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2-phenylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(3-phenylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(4-phenylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2,3-dimethylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2,6-dimethylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(3,4-dimethylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(3,5-dimethylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(3,5-di-t-butylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2,6-diphenylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2,4,6-triphenylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2,4,6-trimethylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(2,4,5,6-tetramethylphenolate)aluminum,bis(2-methyl-8-quinolinolate)(1-naphtholate)aluminum,bis(2-methyl-8-quinolinolate)(2-naphtholate)aluminum,bis(2,4-dimethyl-8-quinolinolate)(2-phenylphenolate) aluminum,bis(2,4-dimethyl-8-quinolinolate)(3-phenylphenolate)aluminum,bis(2,4-dimethyl-8-quinolinolate)(4-phenylphenolate)aluminum,bis(2,4-dimethyl-8-quinolinolate)(3,5-dimethylphenolate)aluminum,bis(2,4-dimethyl-8-quinolinolate)(3,5-di-t-butylphenolate)aluminum,bis(2-methyl-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-8-quinolinolate)aluminum,bis(2,4-dimethyl-8-quinolinolate)aluminum-μ-oxo-bis(2,4-dimethyl-8-quinolinolate)aluminum,bis(2-methyl-4-ethyl-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-4-ethyl-8-quinolinolate)aluminum,bis(2-methyl-4-methoxy-8-quinolinolate)aluminum-1-oxo-bis(2-methyl-4-methoxy-8-quinolinolate)aluminum,bis(2-methyl-5-cyano-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-5-cyano-8-quinolinolate)aluminum,bis(2-methyl-5-trifluoromethyl-8-quinolinolate)aluminum-p-oxo-bis(2-methyl-5-trifluoromethyl-8-quinolinolate)aluminum,bis(10-hydroxybenzo[h]quinoline)beryllium and the like.

The pyridine derivatives are compounds represented by Formula (E-2-1) or(E-2-2) shown below:

wherein R₁ to R₅ are hydrogen or a substituent, and the adjacent groupsmay be combined with each other to form condensed ring(s); G representsa mere bond or an n-valent linkage group; and n is an integer of 2 to 8.

G in Formula (E-2-2) includes, for example, groups shown by thefollowing structural formulas. R(s) in the following structural formulaseach are independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl,phenyl, 1-naphthyl or 2-naphthyl.

The specific examples of the pyridine derivative include, for example,2,5-bis(2,2′-bipyridyl-6-yl)-1,1-dimethyl-3,4-diphenylsilole,2,5-bis(2,2′-bipyridyl-6-yl)-1,1-dimethyl-3,4-dimesitylsilole(hereinafter abbreviated as ET1),9,10-di(2,2′-bipyridyl-6-yl)anthracene,9,10-di(2,2′-bipyridyl-5-yl)anthracene,9,10-di(2,3′-bipyridyl-6-yl)anthracene,9,10-di(2,3′-bipyridyl-5-yl)-2-phenylanthracene,9,10-di(2,2′-bipyridyl-5-yl)-2-phenylanthracene,3,4-diphenyl-2,5-di(2,2′-bipyridyl-6-yl)thiophene,3,4-diphenyl-2,5-di(2,3′-bipyridyl-5-yl)thiophene,6′,6″-di(2-pyridyl)-2,2′:4′,4″:2″:2′″-quaterpyridine and the like.

The phenanthroline derivatives are compounds represented by Formula(E-3-1) or (E-3-2) shown below:

wherein R₁ to R₅ are hydrogen or a substituent, and the adjacent groupsmay be combined with each other to form condensed ring(s); G representsa mere bond or an n-valent linkage group; and n is an integer of 2 to 8.G in Formula (E-3-2) includes, for example, the same groups as explainedin the column of the pyridine derivatives.

The specific examples of the phenanthroline derivative include4,7-diphenyl-1,10-phenanthroline,2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,9,10-di(1,10-phenanthroline-2-yl)anthracene,2,6-di(1,10-phenanthroline-5-yl)pyridine,1,3,5-tri(1,10-phenanthroline-5-yl)benzene,9,9′-difluoro-bis(1,10-phenanthroline-5-yl), bathocuproine,1,3-bis(2-phenyl-1,10-phenanthroline-9-yl)benzene and the like.

In particular, a case where the phenanthroline derivative is used forthe electron transport layer or the electron injection layer shall beexplained. Materials which are excellent in thermal stability and thinfilm forming property are desired in order to obtain stable lightemitting for a long time, and among the phenanthroline derivatives,preferred are compounds in which a substituent itself has athree-dimensional steric structure, compounds having a three-dimensionalsteric structure due to steric repulsion against a phenanthrolineskeleton or an adjacent substituent and compounds obtained by linkingplural phenanthroline skeletons. Further, in the case of the compoundsobtained by linking plural phenanthroline skeletons, more preferred arethe compounds containing a conjugate bond, substituted ornon-substituted aromatic hydrocarbon or substituted or non-substitutedaromatic heterocycle in a linkage unit.

<Cathode in the Organic Electroluminescent Device>

The cathode 108 plays a role of injecting electrons into the emissionlayer 105 via the electron injection layer 107 and the electrontransport layer 106.

A material for forming the cathode 108 shall not specifically berestricted as long as it is a material which can efficiently injectelectrons into the organic layers, and the same materials as thematerials for forming the anode 102 can be used. Among them, preferredare metals such as tin, magnesium, indium, calcium, aluminum, silver,copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium,potassium, and cesium and alloys thereof (magnesium-silver alloys,magnesium-indium alloys and aluminum-lithium alloys such as lithiumfluoride/aluminum alloys) and the like. Lithium, sodium, potassium,cesium, calcium, magnesium and alloys containing the metals having a lowwork function are effective for elevating the electron injectionefficiency to enhance the device characteristics. However, the metalshaving a low work function are usually instable in the air in manycases. In order to solve this issue a method in which a small amount oflithium, cesium or magnesium is doped in an organic layer to use anelectrode having high stability is known. As other dopants, inorganicsalts such as lithium fluoride, cesium fluoride, lithium oxide andcesium oxide can be used as well. However, it shall not be restricted tothe materials.

Further, a preferred example for protecting the electrodes includeslamination of metals such as platinum, gold, silver, copper, iron, tin,aluminum and indium, alloys using these metals, inorganic substancessuch as silica, titania and silicon nitride, polyvinyl alcohol,polyvinyl chloride, hydrocarbon high molecular compounds and the like. Amethod for preparing the electrodes shall not specifically be restrictedas long as the electrodes can conduct electricity and comprisesresistance heating, electron beam, sputtering, ion plating, coating andthe like.

<Binder which May be Used in the Respective Layers>

The materials used for the hole injection layer, the hole transportlayer, the emission layer, the electron transport layer and the electroninjection layer each described above can form alone the respectivelayers, and the materials which are dispersed in solvent-soluble resinssuch as polyvinyl chloride, polycarbonate, polystyrene,poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate,polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbonresins, ketone resins, phenoxy resins, polysulfone, polyamide, ethylcellulose, vinyl acetate resins, ABS resins and polyurethane resins;curing resins such as phenol resins, xylene resins, petroleum resins,urea resins, melamine resins, unsaturated polyester resins, alkydresins, epoxy resins and silicon resins; and the like as high molecularbinders can be used as well.

<Preparing Method for the Organic Electroluminescent Device>

The respective layers constituting the organic electroluminescent devicecan be formed by forming thin films from the materials for constitutingthe respective layers by methods such as a vapor deposition method,resistance heating deposition, electron beam deposition, sputtering, amolecular lamination method, a printing method, a spin cast method, acast method and a coating method. The film thicknesses of the respectivelayers thus formed shall not specifically be restricted and can suitablybe set according to the properties of the materials, and they fallusually in a range of 2 nm to 5000 nm. The film thickness can usually bemeasured by means of a quartz oscillation type film thickness measuringapparatus and the like. When a thin film is formed by a depositionmethod, deposition conditions thereof are varied depending on the kindof the materials, the crystal structure and the aggregate structurewhich are aimed by the film, and the like. In general, the depositionconditions can suitably be set preferably in the ranges of a boatheating temperature of 50 to 400° C., a vacuum degree of 10⁻⁶ to 10⁻³Pa, a deposition rate of 0.01 to 50 nm/second, a substrate temperatureof −150 to +300° C. and a film thickness of 2 nm to 5 μm.

Next, a preparing method for an organic electroluminescent devicecomprising an anode/a hole injection layer/a hole transport layer/anemission layer comprising a host material and a dopant material/anelectron transport layer/an electron injection layer/a cathode shall beexplained as one example of a preparing method for the organicelectroluminescent device. A thin film of an anode material is formed ona suitable substrate by a vapor deposition method and the like toprepare an anode, and then the thin films of a hole injection layer anda hole transport layer are formed on the anode. A host material and adopant material are co-deposited thereon to form a thin film, whereby anemission layer is prepared, and an electron transport layer and anelectron injection layer are formed on the emission layer. Further, athin film comprising a substance for a cathode is formed thereon by avapor deposition method and the like to prepare a cathode, whereby thetargeted organic electroluminescent device is obtained. In preparing theorganic electroluminescent device described above, the preparing ordercan be turned upside down to prepare it as well in the order of thecathode, the electron injection layer, the electron transport layer, theemission layer, the hole transport layer, the hole injection layer andthe anode.

When direct voltage is applied to the organic electroluminescent devicethus obtained, it may be applied with the anode being set to a polarityof + and the cathode being set to a polarity of −, and when a voltage of2 to 40 V is applied, emission can be observed from a transparent ortranslucent electrode side (the anode or the cathode and both). Thisorganic electroluminescent device emits light as well when applying apulse current and an alternating current. A waveform of the alternatingcurrent applied may be optional.

<Application Examples of the Organic Electroluminescent Device>

The present invention can be applied as well to display units equippedwith an organic electroluminescent device, lighting instruments equippedwith an organic electroluminescent device and the like.

The display units or lighting instruments equipped with an organicelectroluminescent device can be produced by such publicly known methodsthat the organic electroluminescent device according to the presentembodiment is connected with publicly known drive apparatuses, and theycan be driven by suitably using publicly known drive methods such asdirect current drive, pulse drive, alternating current drive and thelike.

The display unit includes, for example, panel displays such as colorflat panel displays and flexible displays such as flexible colorelectroluminescent (EL) displays (refer to, for example, JP H10-335066A/1998, JP H15-321546 A/2003, JP H16-281086 A/2004 and the like). Adisplay system of the displays includes, for example, a matrix and/orsegment display system and the like. A matrix display system and asegment display system may be coexistent in the same panel.

A matrix means a state in which pixels for display are two-dimensionallyarranged in a lattice form, a mosaic form and the like, and charactersand images are displayed by aggregate of the pixels. The form and thesize of the pixels are determined by applications. For example, squarepixels having a side of 300 μm or less are usually used for display ofimages and characters in personal computers, monitors and TV. In thecase of a large-sized display such as display panels, pixels having aside of mm order are used. In the case of monochrome display, pixelshaving the same color are arranged, and in the case of color display,red, green and blue pixels are arranged for display. In this case, to betypical, a delta type and a stripe type are available. A drive method ofthis matrix may be either a linear sequential drive method or an activematrix. The linear sequential drive method has the advantage that it hasa simpler structure. However, considering the operation characteristics,the active matrix is more excellent in a certain case, and thereforethis has to be used separately depending on the applications.

In the segment system (type), patterns are formed so that informationsdetermined in advance are displayed, and light is emitted in adetermined area. It includes, for example, display of time andtemperature in digital watches and thermometers, display of operationstates in audio instruments and electromagnetic cookers and display ofpanels in automobiles.

The lighting instrument includes, for example, lighting instruments suchas indoor lighting instruments, backlights for liquid crystal displaysand the like (refer to, for example, JP H15-257621 A/2003, JP H15-277741A/2003, JP H16-119211 A/2004 and the like). The backlights are usedprincipally for a purpose of enhancing a visibility of displayequipments which do not spontaneously emit light, and they are used forliquid crystal displays, watches, audio instruments, car panels, displayboards, indicators and the like. In particular, considering thatbacklights of a conventional system for uses in liquid crystal displays,especially, personal computers in which a reduction in a size is aproblem comprise fluorescent lumps and optical waveguides, so that it isdifficult to reduce in a thickness thereof, a backlight using the lightemitting device according to the present embodiment is characterized bythat it is reduced in a thickness and has a lightweight.

<Synthetic Example of Benzofluorene Compound>

Next, the physical property values of some of the benzofluorenecompounds synthesized are shown in Table 1. The respective physicalproperty values are measured by the following methods. The glasstransition temperatures which are quideposts for the melting points andthe heat resistances were measured by means of Diamond DSC manufacturedby Perkin Elmer Co., Ltd. (measuring conditions: cooling rate 200°C./minute, heating rate 10° C./minute). The UV absorption wavelengthswere measured by means of a V-560 type spectrophotometer manufactured byJASCO Corporation, in which an excitation wavelength was set to 254 nm.

TABLE 1 UV absorption wave- length Solubility maximum (25° C.)Solubility Melting value g/100 ml (25° C.) point (nm) (ethyl g/100 mlCompound (° C.) Tg (° C.) (MeOH) acetate) (toluene)

270 151 360 1   8  

318 155 360 — —

301 140 349 0.2 0.9

61 53 360 — —

64 54 348 — —

284.9 129.2 406 — —

— — 392 — —

It can be found from the above-mentioned results that the glasstransition temperatures of the compound (1-13) and the compound (1-4)are apparently higher than those of the compound (2), (3) and (4). Thecompound (1-13) and the compound (1-4) have higher glass transitiontemperature than those of the compounds (3) and (4), becausesubstitution with alkyl in a five-membered ring of the benzofluoreneskeleton provides the lower glass transition temperature than insubstitution with aryl such as phenyl. The same tendency shall beobserved in the case of the compound (1′-1) in which a substituent on afive-membered ring of the benzofluorene skeleton is phenyl.

Further, it can be found that the compound (1-13) is apparently moreexcellent in solubility in the solvents than the compound (2). This isconsidered to be attributed to the fact that the compound (1-13) has abenzo[c] skeleton. It is estimated that the same tendency shall beobserved in the case of the compound (1-4) and the compound (1′-1)having the benzo[c] skeleton.

In Table 1, the benzofluorene compounds according to the presentinvention are only the compound (1-13), the compound (1-4), the compound(1′-1) and the compound (1′-15) in which Ar¹ and Ar² in Formula (1)described above are phenyl, and when the compounds in which Ar¹ and Ar²are, for example, biphenylyl are applied to a light emitting device,they have the same performances as those of the compound (1-13), thecompound (1-4), the compound (1′-1) and the compound (1′-15). Also, thecompound (1-13) is the compound in which R¹ and R² in Formula (1)described above are 2-naphthyl, and when all the compounds in which R¹and R² are suitably selected from, for example, phenyl, biphenylyl,terphenylyl, quaterphenylyl, naphthyl and phenanthryl are applied to alight emitting device, they have the same performances as that of thecompound (1-13). As a result of further experiment, when the compound(1-4), for example, in which R¹ and R² are selected from biphenylyl isapplied to a light emitting device, it has the same performances as thatof the compound (1-13). Further, the compound (1′-1) is the compound inwhich R¹ and R² in Formula (1′) described above are N,N-diphenylamino,and when all the compounds in which R¹ and R² are suitably selectedfrom, for example, N,N-di(biphenylyl)amino and N,N-dinaphthylamino areapplied to a light emitting device, they have the same performances asthat of the compound (1′-1). Also, the compound (1′-15) is the compoundin which R¹ in Formula (1′) described above is N,N-diphenylamino, andwhen all the compounds in which R¹ is suitably selected from, forexample, N,N-di(biphenylyl)amino and N,N-dinaphthylamino are applied toa light emitting device, they have the same performances as that of thecompound (1′-15).

The synthetic examples of the compound (1-13), the compound (1-4), thecompound (2), the compound (3), the compound (4), the compound (1′-1)and the compound (1′-15) shall be explained below.

<Synthetic Example of the Compound (1-13)>

7,7-Diphenyl-5,9-bis(trifluoromethanesulfonyloxy)-7H-benzo[c]fluorene6.66 g and 2-naphthyleneboronic acid 5.16 g were dissolved in 100 ml ofa mixed solvent of tetrahydrofuran and isopropyl alcohol(tetrahydrofuran/isopropyl alcohol=1/4 (volume ratio)) under nitrogenatmosphere, and 1.16 g of tetrakis(triphenylphosphine)palladium (0) wasadded thereto, and the mixture was stirred for 5 minutes. Then, 12.7 gof potassium phosphate was added thereto, and the mixture was refluxedfor 4 hours. After finishing the reaction, 50 ml of the solvent wasremoved. Water 100 ml was added thereto, and the precipitate wasfiltered. The precipitate was further washed with water and methanol toobtain a crude product of the compound (1-13). The crude product wassubjected to column refining (solvent: heptane/toluene=3/1 (volumeratio)) with silica gel and then refined by sublimation to obtain 5.0 gof the targeted compound (1-13) (yield: 80.5%).

The structure of the compound (1-13) was confirmed by an MS spectrum andNMR measurement.

¹H-NMR (CDCl₃) σ=8.93 (d, 1H), 8.53 (d, 1H), 8.06 to 8.04 (m, 2H), 7.93to 7.21 (m, 28H)

<Synthetic Example of the Compound (1-4)>

5,9-Dibrome-7,7-diphenyl-7H-benzo[c]fluorene 5.26 g and biphenyl boronicacid 4.36 g were dissolved in 50 ml of a mixed solvent of toluene andethanol (toluene/ethanol=4/1 (volume ratio)) under nitrogen atmosphere,and 0.69 g of tetrakis(triphenylphosphine)palladium (0) was addedthereto, and the mixture was stirred for 5 minutes. Then, 20 ml of 2Msodium hydrogencarbonate aqueous solution was added thereto, and themixture was refluxed for 8 hours. After finishing the heating, thereaction mixture was cooled, and the organic layer was isolated andwashed with saturated saline and then dried with anhydrous magnesiumsulfate. Then, the desiccant agent was removed and the solvent wasdistilled away under reduced pressure to obtain a solid material. Thesolid material was subjected to column refining (solvent:heptane/toluene=3/1 (volume ratio)) with silica gel and then refined bysublimation to obtain 3.9 g of the targeted compound (1-4) (yield: 58%).

The structure of the compound (1-4) was confirmed by an MS spectrum andNMR measurement.

¹H-NMR (CDCl₃) σ=8.91 (d, 1H), 8.49 (d, 1H), 8.11 (d, 1H), 7.79 to 7.77(m, 2H), 7.73 to 7.20 (m, 31H)

<Synthetic Example of the Compound (2)>

Synthesis of 3,9-dinaphthalene-2-yl-11,11-diphenyl-11H-benzo[a]fluorenewas carried out by the following method.

11,11-Diphenyl-3,9-bis(trifluoromethanesulfonyloxy)-11H-benzo[a]fluorene6.66 g and 2-naphthyleneboronic acid 5.16 g were dissolved in 100 ml ofa mixed solvent of tetrahydrofuran and isopropyl alcohol(tetrahydrofuran/isopropyl alcohol=1/4 (volume ratio)) under nitrogenatmosphere, and 1.16 g of tetrakis(triphenylphosphine)palladium (0) wasadded thereto, and the mixture was stirred for 5 minutes. Then, 12.7 gof potassium phosphate was added thereto, and the mixture was refluxedfor 4 hours. After finishing the reaction, 50 ml of the solvent wasremoved. Water 100 ml was added thereto, and the precipitate wasfiltered. The precipitate was further washed with water and methanol toobtain a crude product of the compound (2). The crude product wassubjected to column refining (solvent: heptane/toluene=3/1 (volumeratio)) with silica gel and then refined by sublimation to obtain 4.2 gof the targeted compound (2) (yield: 67.6%).

The structure of the compound (2) was confirmed by an MS spectrum andNMR measurement.

¹H-NMR (CDCl₃) σ=8.23 (d, 1H), 8.1 to 8.08 (m, 3H), 7.98 to 7.67 (m,14H), 7.51 to 7.42 (m, 8H), 7.27 to 7.22 (m, 6H)

<Synthetic Example of the Compound (3)>

Synthesis of 7,7-Dihexyl-5,9-di-naphthalene-2-yl-7H-benzo[c]fluorene wascarried out by the following method.

5,9-Dibromo-7,7-dihexyl-7H-benzo[c]fluorene 5.42 g and 2-naphtyleneboronic acid 3.78 g were dissolved in 50 ml of a mixed solvent oftoluene and ethanol (toluene/ethanol=4/1 (volume ratio)) under nitrogenatmosphere, and 0.69 g of tetrakis(triphenylphosphine)palladium (0) wasadded thereto, and the mixture was stirred for 5 minutes. Then, 20 ml of2M sodium hydrogencarbonate aqueous solution was added thereto, and themixture was refluxed for 7 hours. After finishing the heating, thereaction mixture was cooled, and the organic layer was isolated andwashed with saturated saline and then dried with anhydrous magnesiumsulfate. Then, the desiccant agent was removed and the solvent wasdistilled away under reduced pressure to obtain a crude product. Thecrude product was subjected to column refining (solvent:heptane/toluene=3/1 (volume ratio)) with silica gel and then refined bysublimation to obtain 4.4 g of the targeted compound (3) (yield: 69%).

The structure of the compound (3) was confirmed by an MS spectrum andNMR measurement.

¹H-NMR (CDCl₃) σ=8.89 (d, 1H), 8.46 (d, 1H), 8.17 to 7.25 (m, 20H), 2.20to 2.10 (m, 4H), 1.14 to 1.00 (m, 12H), 0.76 to 0.69 (m, 10H)

<Synthetic Example of the Compound (4)>

Synthesis of 11,11-Dihexyl-3,9-di-naphthalene-2-yl-11H-benzo[a]fluorenewas carried out by the following method.

11,11-Dihexyl-3,9-bis(trifluoromethanesulfonyloxy)-11H-benzo[a]fluorene6.81 g and 2-naphthyleneboronic acid 4.13 g were dissolved in 100 ml ofa mixed solvent of tetrahydrofuran and isopropyl alcohol(tetrahydrofuran/isopropyl alcohol=1/4 (volume ratio)) under nitrogenatmosphere, and 1.16 g of tetrakis(triphenylphosphine)palladium (0) wasadded thereto, and the mixture was stirred for 5 minutes. Then, 12.7 gof potassium phosphate was added thereto, and the mixture was refluxedfor 5 hours. After finishing the reaction, 50 ml of the solvent wasremoved. Water 100 ml was added thereto, and the precipitate wasfiltered. The precipitate was further washed with water and methanol toobtain a crude product of the compound (4). The crude product wassubjected to column refining (solvent: heptane/toluene=5/1 (volumeratio)) with silica gel and then refined by sublimation to obtain 5.1 gof the targeted compound (4) (yield: 80%).

The structure of the compound (4) was confirmed by an MS spectrum andNMR measurement.

¹H-NMR (CDCl₃) σ=8.34 (d, 1H), 8.31 (d, 1H), 8.23 (d, 1H), 8.15 (d, 1H),8.01 to 7.87 (m, 12H), 7.80 to 7.77 (m, 2H), 7.56 to 7.49 (m, 4H), 2.60to 2.33 (m, 4H), 1.03 to 0.93 (m, 12H), 0.71 to 0.68 (t, 6H), 0.60 to0.48 (m, 4H)

<Synthetic Example of the Compound (1′-1)>

5,9-Dibromo-7,7-diphenyl-7H-benzo[c]fluorene 2.5 g and diphenylamine 1.6g were dissolved in 100 ml of dehydrated xylene under nitrogenatmosphere, and palladium acetate 1.5 mg, sodium t-butoxide 0.98 g andtri(t-butyl)phosphine 14 mg was added thereto and refluxed for 4 hours.After finishing the reaction, water 100 ml was added thereto, and theorganic layer was washed with water in a separating funnel. The aqueouslayer was removed, and then the organic layers were put together andconcentrated by means of a rotary evaporator to obtain a crude product.The crude product was subjected to column refining (solvent:heptane/toluene=3/1 (volume ratio)) with silica gel and then refined bysublimation to obtain 450 mg of the targeted compound (1′-1) (yield:13%)

The structure of the compound (1′-1) was confirmed by an MS spectrum andNMR measurement.

¹H-NMR (CDCl₃) σ=8.70 (d, 1H), 8.16 (d, 1H), 8.02 (d, 1H), 7.56 (t, 1H),7.37 to 7.34 (m, 2H), 7.58 to 6.86 (m, 32H)

<Synthetic Example of the Compound (1′-15)>

5-Bromo-9-phenyl-7,7-diphenyl-7H-benzo[c]fluorene 1.4 g anddiphenylamine 0.5 g were dissolved in 30 ml of dehydrated xylene undernitrogen atmosphere, and palladium acetate 3.0 mg, sodium t-butoxide0.89 g and tri(t-butyl)phosphine 15 mg was added thereto and refluxedfor 4 hours. After finishing the reaction, water 30 ml was addedthereto, and the organic layer was washed with water in a separatingfunnel. The aqueous layer was removed, and then the organic layers wereput together and concentrated by means of a rotary evaporator to obtain1.1 g of the targeted compound (1′-15) (yield: 64%). The structure ofthe compound (1′-15) was confirmed by an MS spectrum.

The other benzofluorene compounds of the present invention can besynthesized according to the synthetic examples described above bysuitably selecting the compounds of the raw materials.

EXAMPLES

Organic electroluminescent devices according to Examples 1, 2, 3, 4 and5 and Comparative Example 1, 2, 3 and 4 were prepared to measure voltage(V) which is a characteristic in emission of 100 cd/m², current density(mA/cm²), luminous efficiency (lm/W), current efficiency (cd/A),emission wavelength (nm), chromaticity (x, y), external quantumefficiency (%) and luminance retention rate (%) after 200 hours in aninitial luminance of 1000 cd/m² or elapsed time at luminance retentionrate 70% in an initial luminance of 2000 cd/m². Examples 1, 2, 3, 4 and5 and Comparative Example 1, 2, 3 and 4 shall be explained below indetails.

The material compositions of the respective layers in the organicelectroluminescent devices prepared in Examples 1, 2, 3 and 4 andComparative Example 1, 2 and 3 are shown in the following Table 2.

TABLE 2 Hole Hole Electron injection transport transport layer layerHost Dopant layer Example 1 CuPc NPD Compound D1 ALQ 1-13 Example 2 CuPcNPD Compound D1 ET1 1-13 Example 3 CuPc NPD Compound D1 ALQ 1-4 Example4 CuPc NPD Compound D1 ET2 1-4 Example 5 CuPc NPD BH1 Compound ALQ 1′-1Comparative CuPc NPD Compound D1 ALQ Example 1 2 Comparative CuPc NPDCompound D1 ALQ Example 2 3 Comparative CuPc NPD Compound D1 ET2 Example3 3 Comparative CuPc NPD Compound D1 ET2 Example 4 4

In Table 2, Compound (1-13), Compound (1-4), Compound (1′-1), Compound(2), Compound (3) and Compound (4) each show Compound (1-13), Compound(1-4), Compound (1′-1), Compound (2), Compound (3) and Compound (4) inTable 1. In Table 2, CuPc is copper phthalocyanine; NPD isN,N′-di(1-naphthyl)-N,N′-diphenylbenzidine; D1 isN,N,N′,N′-tetra(4-biphenylyl)-4,4-diaminostilbene; ALQ istris(8-quinolinolate)aluminum; ET1 is2,5-bis(2,2′-bipyridyl-6-yl)-1,1-dimethyl-3,4-dimesitylsilole; ET2 is2,21,2″-(1,3,5-phenylene)tris(1-phenyl-1H-benzimidazole); and BH1 is9-phenyl-10-(6-[1,1′:3′,1″]terphenyl-5′-yl-naphthalene-2-yl)-anthracene.They each have the following chemical structural formulas.

Example 1

A glass substrate of 26 mm×28 mm×0.7 mm on which ITO was deposited in athickness of 150 nm was used as a transparent substrate. Thistransparent substrate was fixed on a substrate holder of a commercialdeposition system, and loaded therein were a molybdenum-made boat fordeposition containing CuPc, a molybdenum-made boat for depositioncontaining NPD, a molybdenum-made boat for deposition containing thecompound (1-13), a molybdenum-made boat for deposition containing D1, amolybdenum-made boat for deposition containing ALQ, a molybdenum-madeboat for deposition containing lithium fluoride and a tungsten-made boatfor deposition containing Aluminum.

A vacuum chamber was reduced in pressure up to 5×10⁻⁴ Pa, and the boatfor deposition containing CuPc was heated to deposit it in a layerthickness of 20 nm, whereby a hole injection layer was formed. Then, theboat for deposition containing NPD was heated to deposit it in a layerthickness of 30 nm, whereby a hole transport layer was formed. Next, themolybdenum-made boat for deposition containing Compound (1-13) and themolybdenum-made boat for deposition containing D1 were heated toco-deposit both compounds in a layer thickness of 30 nm, whereby anemission layer was formed. In this regard, a doping concentration of D1was about 5% by weight. Next, the boat for deposition containing ALQ washeated to deposit it in a layer thickness of 20 nm, whereby an electrontransport layer was formed. The deposit rates of the layers describedabove were 0.01 to 1 nm/second.

Thereafter, the boat for deposition containing lithium fluoride washeated to deposit it at a deposition rate of 0.003 to 0.1 nm/second sothat a layer thickness was 0.5 nm, and then the boat for depositioncontaining aluminum was heated to deposit it at a deposition rate of0.01 to 10 nm/second so that a layer thickness was 100 nm, whereby anorganic EL device was obtained.

With the ITO electrode set to an anode and the lithium fluoride/aluminumelectrode set to a cathode, the characteristics in emission of 100 cd/m²were measured to find that the voltage was 4.8 V; the current densitywas 1.7 mA/cm²; the luminous efficiency was 3.7 μm/W; the currentefficiency was 5.7 cd/A; the emission wavelength was 455 nm; and thechromaticity was (0.145, 0.162). Further, the external quantumefficiency was 5.0%, and the current density in the external quantumefficiency was 10 mA/cm². A constant current operation test was carriedout at current density for obtaining an initial luminance of 1000 cd/m²to find that the luminance retention rate was 89.0% after 200 hourspassed.

Example 2

An organic EL device was obtained by a method according to Example 1,except that ALQ used for the electron transport layer in Example 1 waschanged to ET1. With the ITO electrode set to an anode and the lithiumfluoride/aluminum electrode set to a cathode, the characteristics inemission of 100 cd/m² were measured to find that the voltage was 3.7 V;the current density was 1.6 mA/cm²; the luminous efficiency was 5.4μm/W; the current efficiency was 6.3 cd/A; the emission wavelength was455 nm; and the chromaticity was (0.145, 0.168). Further, the externalquantum efficiency was 4.9%, and the current density in the externalquantum efficiency was 10 mA/cm². The constant current operation testwas carried out at current density for obtaining an initial luminance of1000 cd/m² to find that the luminance retention rate was 76.2% after 200hours passed.

Example 3

A glass substrate of 26 mm×28 mm×0.7 mm on which ITO was deposited in athickness of 150 nm was used as a transparent substrate. Thistransparent substrate was fixed on a substrate holder of a commercialdeposition system, and loaded therein were a molybdenum-made boat fordeposition containing CuPc, a molybdenum-made boat for depositioncontaining NPD, a molybdenum-made boat for deposition containing thecompound (1-4), a molybdenum-made boat for deposition containing D1, amolybdenum-made boat for deposition containing ALQ, a molybdenum-madeboat for deposition containing lithium fluoride and a tungsten-made boatfor deposition containing Aluminum.

A vacuum chamber was reduced in pressure up to 5×10⁻⁴ Pa, and the boatfor deposition containing CuPc was heated to deposit it in a layerthickness of 50 nm, whereby a hole injection layer was formed. Then, theboat for deposition containing NPD was heated to deposit it in a layerthickness of 30 nm, whereby a hole transport layer was formed. Next, themolybdenum-made boat for deposition containing Compound (1-4) and themolybdenum-made boat for deposition containing D1 were heated toco-deposit both compounds in a layer thickness of 35 nm, whereby anemission layer was formed. In this regard, a doping concentration of D1was about 5% by weight. Next, the boat for deposition containing ALQ washeated to deposit it in a layer thickness of 15 nm, whereby an electrontransport layer was formed. The deposit rates of the layers describedabove were 0.01 to 1 nm/second.

Thereafter, the boat for deposition containing lithium fluoride washeated to deposit it at a deposition rate of 0.003 to 0.1 nm/second sothat a layer thickness was 0.5 nm, and then the boat for depositioncontaining aluminum was heated to deposit it at a deposition rate of0.01 to 10 nm/second so that a layer thickness was 100 nm, whereby anorganic EL device was obtained.

With the ITO electrode set to an anode and the lithium fluoride/aluminumelectrode set to a cathode, the characteristics in emission of 100 cd/m²were measured to find that the voltage was 4.6 V; the current densitywas 1.9 mA/cm²; the luminous efficiency was 3.6 μm/W; the currentefficiency was 5.3 cd/A; the emission wavelength was 455 nm; and thechromaticity was (0.141, 0.140). Further, the external quantumefficiency was 5.1%, and the current density in the external quantumefficiency was 2 mA/cm². A constant current operation test was carriedout at current density for obtaining an initial luminance of 2000 cd/m²to find that the elapsed time at luminance retention rate 70% was 165hours.

Example 4

An organic EL device was obtained by a method according to Example 3,except that ALQ used for the electron transport layer in Example 3 waschanged to ET2. With the ITO electrode set to an anode and the lithiumfluoride/aluminum electrode set to a cathode, the characteristics inemission of 100 cd/m² were measured to find that the voltage was 4.4 V;the current density was 1.8 mA/cm²; the luminous efficiency was 4.0μm/W; the current efficiency was 5.6 cd/A; the emission wavelength was455 nm; and the chromaticity was (0.141, 0.142). Further, the externalquantum efficiency was 5.4%, and the current density in the externalquantum efficiency was 2 mA/cm². The constant current operation test wascarried out at current density for obtaining an initial luminance of2000 cd/m² to find that the elapsed time at luminance retention rate 70%was 88 hours.

Example 5

An organic EL device was obtained by a method according to Example 1,except that the compound (1-13) used as the host in Example 1 waschanged to BH1 and that D1 used as the dopant was changed to thecompound (1′-1). With the ITO electrode set to an anode and the lithiumfluoride/aluminum electrode set to a cathode, the characteristics inemission of 100 cd/m² were measured to find that the voltage was 5.3 V;the current density was 1.8 mA/cm²; the luminous efficiency was 3.3μm/W; the current efficiency was 5.5 cd/A; the emission wavelength was460 nm; and the chromaticity was (0.140, 0.159). Further, the externalquantum efficiency was 5.2%, and the current density in the externalquantum efficiency was 10 mA/cm². The constant current operation testwas carried out at current density for obtaining an initial luminance of1000 cd/m² to find that the luminance retention rate was 90.0% after 200hours passed.

Comparative Example 1

An organic EL device was obtained by a method according to Example 1,except that the compound (1-13) used as the host in Example 1 waschanged to the compound (2). With the ITO electrode set to an anode andthe lithium fluoride/aluminum electrode set to a cathode, thecharacteristics in emission of 100 cd/m² were measured to find that thevoltage was 5.2 V; the current density was 1.7 mA/cm²; the luminousefficiency was 3.5 μm/W; the current efficiency was 5.8 cd/A; theemission wavelength was 456 nm; and the chromaticity was (0.145, 0.168).Further, the external quantum efficiency was 4.8%, and the currentdensity in the external quantum efficiency was 10 mA/cm². The constantcurrent operation test was carried out at current density for obtainingan initial luminance of 1000 cd/m² to find that the luminance retentionrate was 88.5% after 200 hours passed.

Comparative Example 2

An organic EL device was obtained by a method according to Example 3,except that the compound (1-4) used as the host in Example 3 was changedto the compound (3). With the ITO electrode set to an anode and thelithium fluoride/aluminum electrode set to a cathode, thecharacteristics in emission of 100 cd/m² were measured to find that thevoltage was 5.3 V; the current density was 19.5 mA/cm²; the luminousefficiency was 0.31 lm/W; the current efficiency was 0.5 cd/A; theemission wavelength was 520 nm; and the chromaticity was (0.239, 0.523).Further, the external quantum efficiency was 0.2%, and the currentdensity in the external quantum efficiency was 17.2 mA/cm². Also, theorganic EL device has very low efficiency because it has ALQluminescence.

Comparative Example 3

An organic EL device was obtained by a method according to Example 4,except that the compound (1-4) used as the host in Example 4 was changedto the compound (3). With the ITO electrode set to an anode and thelithium fluoride/aluminum electrode set to a cathode, thecharacteristics in emission of 100 cd/m² were measured to find that thevoltage was 4.7 V; the current density was 2.6 mA/cm²; the luminousefficiency was 2.6 lm/W; the current efficiency was 3.8 cd/A; theemission wavelength was 450 nm; and the chromaticity was (0.142, 0.114).Further, the external quantum efficiency was 4.6%, and the currentdensity in the external quantum efficiency was 3.2 mA/cm². The constantcurrent operation test was carried out at current density for obtainingan initial luminance of 2000 cd/m² to find that the elapsed time atluminance retention rate 70% was 1 hour.

Comparative Example 4

An organic EL device was obtained by a method according to Example 4,except that the compound (1-4) used as the host in Example 4 was changedto the compound (4). With the ITO electrode set to an anode and thelithium fluoride/aluminum electrode set to a cathode, thecharacteristics in emission of 100 cd/m² were measured to find that thevoltage was 4.8 V; the current density was 2.4 mA/cm²; the luminousefficiency was 2.7 lm/W; the current efficiency was 4.2 cd/A; theemission wavelength was 450 nm; and the chromaticity was (0.142, 0.120).Further, the external quantum efficiency was 4.7%, and the currentdensity in the external quantum efficiency was 2.2 mA/cm². The constantcurrent operation test was carried out at current density for obtainingan initial luminance of 2000 cd/m² to find that the elapsed time atluminance retention rate 70% was 29 hours.

The performance evaluation results of the organic electroluminescentdevices prepared in Examples 1, 2, 3, 4 and 5 and Comparative Example 1,2, 3 and 4 are summarized in the following Table 3.

TABLE 3 Life Elapsed time External luminance at luminance quantumretention rate retention rate Characteristics in emission of 100 cd/m²efficiency after 200 hours 70% (initial Current Luminous CurrentEmission Current passed (initial luminance: Voltage density efficiencyefficiency wavelength Chromaticity density luminance: 2000 cd/m²) VmA/cm² lm/W cd/A nm (x, y) % mA/cm² 1000 cd/m²) % hour Ex. 1 4.8 1.7 3.75.7 455 0.145, 0.162 5.0 10 89.0 — Ex. 2 3.7 1.6 5.4 6.3 455 0.145,0.168 4.9 10 76.2 — Ex. 3 4.6 1.9 3.6 5.3 455 0.141, 0.140 5.1 2 — 165Ex. 4 4.4 1.8 4.0 5.6 455 0.141, 0.142 5.4 2 — 88 Ex. 5 5.3 1.8 3.3 5.5460 0.140, 0.159 5.2 10 90.0 — Comp. 5.2 1.7 3.5 5.8 456 0.145, 0.1684.8 10 88.5 — Ex. 1 Comp. 5.3 19.5 0.3 0.5 520 0.239, 0.523 0.2 17.2 — —Ex. 2 Comp. 4.7 2.6 2.6 3.8 450 0.142, 0.114 4.6 3.2 — 1 Ex. 3 Comp. 4.82.4 2.7 4.2 450 0.140, 0.120 4.7 2.2 — 29 Ex. 4

It can be found from the result of Comparative Examples 2, 3 and 4 thatsubstitution with alkyl in a five-membered ring of the benzofluoreneskeleton provides low luminous efficiency and current efficiency of theEL devices, and short life.

INDUSTRIAL APPLICABILITY

According to the preferred embodiment of the present invention, broaderwidth in selecting the solvents in the synthesis makes it possible toenhance freedom in the synthesis of the compounds and employ freelayer-forming means in forming the layers of the light emitting device.Further, capable of being provided are an organic electroluminescentdevice having better performances in at least one of heat resistance,luminous efficiency, current efficiency, device life and externalquantum efficiency, a display unit equipped with the same, a lightinginstrument equipped with the same and the like.

BRIEF EXPLANATION OF THE DRAWING

FIG. 1 is an outline cross-sectional drawing showing the organicelectroluminescent device according to the present embodiment.

EXPLANATIONS OF CODES

-   100 Organic electroluminescent device-   101 Substrate-   102 Anode-   103 Hole injection layer-   104 Hole transport layer-   105 Emission layer-   106 Electron transport layer-   107 Electron injection layer-   108 Cathode

1. A benzofluorene compound represented by the following Formula (1):

(wherein Ar¹ and Ar² are aryl which may be substituted; R¹ and R² eachare independently hydrogen, alkyl which may be substituted, cycloalkylwhich may be substituted or aryl which may be substituted, and at leastone of R¹ and R² is aryl which may be substituted).
 2. The benzofluorenecompound as described in claim 1, wherein Ar¹ and Ar² are aryl having 6to 30 carbon atoms which may be substituted; R¹ and R² each areindependently hydrogen, alkyl having 1 to 24 carbon atoms which may besubstituted, cycloalkyl having 3 to 12 carbon atoms which may besubstituted or aryl having 6 to 30 carbon atoms which may besubstituted, and at least one of R¹ and R² is aryl having 6 to 30 carbonatoms which may be substituted; and substituents in Ar¹, Ar², R¹ and R²each are independently alkyl having 1 to 24 carbon atoms, cycloalkylhaving 3 to 12 carbon atoms or aryl having 6 to 30 carbon atoms.
 3. Thebenzofluorene compound as described in claim 1, wherein Ar¹ and Ar² arearyl having 6 to 16 carbon atoms which may be substituted; R¹ and R² arearyl having 6 to 24 carbon atoms which may be substituted; andsubstituents in Ar¹, Ar², R¹ and R² each are independently alkyl having1 to 12 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or arylhaving 6 to 20 carbon atoms.
 4. The benzofluorene compound as describedin claim 1, wherein Ar¹ and Ar² are aryl having 6 to 12 carbon atomswhich may be substituted; R¹ and R² are aryl having 6 to 20 carbon atomswhich may be substituted; and substituents in Ar¹, Ar², R¹ and R² eachare independently methyl, ethyl, propyl, t-butyl, cyclobutyl,cyclopentyl, cyclohexyl, phenyl, biphenylyl or naphthyl.
 5. Thebenzofluorene compound as described in claim 1, wherein Ar¹ and Ar² eachare independently phenyl or biphenylyl; and R¹ and R² each areindependently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthylor phenanthryl.
 6. The benzofluorene compound as described in claim 1,wherein Ar¹ and Ar² are aryl having 6 to 16 carbon atoms which may besubstituted; one of R¹ and R² is hydrogen, and the other is aryl having6 to 24 carbon atoms which may be substituted; and substituents in Ar¹,Ar², R¹ and R² each are independently alkyl having 1 to 12 carbon atoms,cycloalkyl having 3 to 6 carbon atoms or aryl having 6 to 20 carbonatoms.
 7. The benzofluorene compound as described in claim 1, whereinAr¹ and Ar² are aryl having 6 to 12 carbon atoms which may besubstituted; one of R¹ and R² is hydrogen, and the other is aryl having6 to 20 carbon atoms which may be substituted; and substituents in Ar¹,Ar², R¹ and R² each are independently methyl, ethyl, propyl, t-butyl,cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenylyl or naphthyl. 8.The benzofluorene compound as described in claim 1, wherein Ar¹ and Ar²each are independently phenyl or biphenylyl; and one of R¹ and R² ishydrogen, and the other is phenyl, biphenylyl, terphenylyl,quaterphenylyl, naphthyl or phenanthryl.
 9. The benzofluorene compoundas described in claim 1, wherein Ar¹ and Ar² are phenyl; R¹ is4-biphenylyl, and R² is 4-biphenylyl.
 10. The benzofluorene compound asdescribed in claim 1, wherein Ar¹ and Ar² are phenyl; R¹ is 2-naphthyl,and R² is 2-naphthyl.
 11. The benzofluorene compound as described inclaim 1, wherein Ar¹ and Ar² are phenyl; R¹ is 4-biphenylyl, and R² is2-naphthyl.
 12. The benzofluorene compound as described in claim 1,wherein Ar¹ and Ar² are phenyl; R¹ is 2-naphthyl, and R² is4-biphenylyl.
 13. A benzofluorene compound represented by the followingFormula (1′):

(wherein Ar¹ and Ar² are aryl which may be substituted; R¹ isdiarylamino having aryl which may be substituted; and R² is hydrogen,alkyl which may be substituted, cycloalkyl which may be substituted,aryl which may be substituted or diarylamino having aryl which may besubstituted).
 14. The benzofluorene compound as described in claim 13,wherein Ar¹ and Ar² are aryl having 6 to 30 carbon atoms which may besubstituted; R¹ is diarylamino having aryl having 6 to 30 carbon atomswhich may be substituted; R² is hydrogen, alkyl having 1 to 24 carbonatoms which may be substituted, cycloalkyl having 3 to 12 carbon atomswhich may be substituted, aryl having 6 to 30 carbon atoms which may besubstituted or diarylamino having aryl having 6 to 30 carbon atoms whichmay be substituted; and substituents in Ar¹, Ar², R¹ and R² each areindependently alkyl having 1 to 24 carbon atoms, aryl having 6 to 30carbon atoms or heteroaryl having 2 to 30 carbon atoms.
 15. Thebenzofluorene compound as described in claim 13, wherein Ar¹ and Ar² arearyl having 6 to 16 carbon atoms which may be substituted; R¹ isdiarylamino having aryl having 6 to 16 carbon atoms which may besubstituted; R² is hydrogen, aryl having 6 to 24 carbon atoms which maybe substituted or diarylamino having aryl having 6 to 16 carbon atomswhich may be substituted; and substituents in Ar¹, Ar², R¹ and R² eachare independently alkyl having 1 to 12 carbon atoms, aryl having 6 to 12carbon atoms or heteroaryl having 2 to 10 carbon atoms.
 16. Thebenzofluorene compound as described in claim 13, wherein Ar¹ and Ar² arearyl having 6 to 12 carbon atoms which may be substituted; R¹ isdiarylamino having aryl having 6 to 12 carbon atoms which may besubstituted; R² is hydrogen, aryl having 6 to 20 carbon atoms which maybe substituted or diarylamino having aryl having 6 to 12 carbon atomswhich may be substituted; and substituents in Ar¹, Ar², R¹ and R² eachare independently methyl, ethyl, propyl, t-butyl, phenyl, biphenylyl,naphthyl, pyridyl or thienyl.
 17. The benzofluorene compound asdescribed in claim 13, wherein Ar¹ and Ar² each are independently phenylor biphenylyl; R¹ is diphenylamino, dibiphenylamino, dinaphthylamino orphenylnaphthylamino; and R² is phenyl, biphenylyl, terphenylyl,quaterphenylyl, naphthyl, phenanthryl, diphenylamino, dibiphenylamino,dinaphthylamino or phenylnaphthylamino.
 18. The benzofluorene compoundas described in claim 13, wherein Ar¹ and Ar² are phenyl; and R¹ and R²are diphenylamino.
 19. A material for an emission layer in a lightemitting device and which contains the benzofluorene compound asdescribed in claim
 1. 20. The material for an emission layer asdescribed in claim 19, further containing at least one selected from thegroup consisting of perylene derivatives, borane derivatives,amine-containing styryl derivatives, aromatic amine derivatives,coumarin derivatives, pyran derivatives, iridium complexes and platinumcomplexes.
 21. An organic electroluminescent device comprising a pair ofelectrodes comprising an anode and a cathode and an emission layer whichis disposed between a pair of the electrodes and which contains thematerial for an emission layer as described in claim
 19. 22. The organicelectroluminescent device as described in claim 21, further comprisingan electron transport layer and/or an electron injection layer disposedbetween the cathode and the emission layer, wherein at least one of theelectron transport layer and electron injection layer contains at leastone selected from the group consisting of quinolinol metal complexes,pyridine derivatives and phenanthroline derivatives.
 23. A display unitcomprising the organic electroluminescent device as described in claim21.
 24. A lighting instrument comprising the organic electroluminescentdevice as described in claim
 21. 25. A material for an emission layer ina light emitting device and which contains the benzofluorene compound asdescribed in claim 13.